LEWIS-BASE MEDIATED FRAGMENTATION OF POLYMERIC TRANSITION METAL DICARBOXYLATES

Thesis Submitted to the Mahatma Gandhi University in Partial Fulfilment of the Requirements for the Award of the Degree of

Doctor of Philosophy in Chemistry Under the Faculty of Science

By

Meenakumary S.

Supervising Teacher

Professor M. Padmanabhan

School of Chemical Sciences Mahatma Gandhi University Kottayam, Kerala, India February 2005

DECLARATION
I hereby declare that this thesis entitled Lewis-base Mediated Fragmentation of Polymeric Transition Metal Dicarboxylates is an authentic record of the research work carried out by me under the supervision of Dr. M. Padmanabhan, Professor and Director, School of Chemical Sciences, Mahatma Gandhi University, Kottayam, Kerala and that no part of this thesis has been submitted earlier for the award of any other degree or diploma.

Kottayam 02-02-2005

Meenakumary S

Acknowledgements
I h u e great pleasure to record my deepest gratitude and heartfelt
thanks to my Supermimy Temlzer, Prof: CDr). M.Padmanabhnn, Director, S h o a l

of Chemical Sciems, M a h d m G a n d h Urtiversity, Kottayam, for hs invaluable g u i d m e thrw~ghout my research w r k

I wish to express my grntrntrtude to Prof: 0.V. N, Rajasekharan h'uai,

Former Director, School o f Chemical Sciences and Vice Chairman, University

Grants Cornmisston for his valuabie s u g g e s t i o r ~ .
I siric:t.rely acknou)l~dge the help re&&

by Dr. K. K. M. Yuswfl arld his

research group, Cochrn University oJ SnSnenm and Teduwlogy, Cocltin. to cdrry out the nzqnetic ~neusur-ernents. 1 w i s l i to q r e s s my sincere thmdcs to the

Heuds o f RegiotLal Research Laboratonj, Thimruvanw~tkurnm, Regior~aI

Sophisticated

Instrumenfntior~ Centres

at

LIT Madras, IlT Mumbai,

Department of Chemistry, NEHU Shillong, Sopl~isttcated Instrumerdation

Centre for Applied Research and Testing, Charudar Vidyamandal, Vallabha

Nagar, Gujarat and CDRI, Lucknow, for providing facilities for the analytimi
measurements.
I express t r y thanks to all the Administrative, Teclmical, Library arid

Laboratoty staff o f School of Chen~icalSciences for all the aduices and

f my utmost co-operation extended by them to me during the course o

reseurch work.
I &o
r.xpress my thnnks to Mr. M. K. Vijuyakurrmr and Mr. K.A. JWS,

ScSclwol uf Chemical S5errces for t k neat trunngs. I arrl also Ihur kfil to the staff;
Universriy Computer Cer~tre Jor their slncere help received dunng the period

of this research work.

I urn very rrtuch yrute&I to all rny coIleagues, lab mates and friends

in School of Chemicnl Sciences for their support and co-operation for

successfrr I con~pletiotl qf this research work.

express my gratitude to the staff of

the Iibraies of the

hl.C;. Ur~~lccrsity, Kuttoycir?~ the Cochv<Unrzem'ty, Chchn and tlze DSc, Banglore.

The help rendered by Mr. Murali, Mr. R a p Vargese and Mr. Unnikrishnan,

of Ur~iuersrty Libray i s sincerely acknoutledged.

Mr. k: V Sliibu, Mr. Unrii ard other members, M/ S. Afinitek Computers, Opp. 11f.G. University, for the effort they
I express my sincere thanks to

have taken in the preparati~nof thts thesis.

I

ternerrher with deep

/love and

m p a d . mu father,

the late

Shri Raveendran Unnifhun P.K, for his advice, care, love and affection I
recel ued.

I c?.vpress my grutip~deto my mother Smt. Sarala Devi Arnma, far her

rol~stcrrltirrspiraiiur~and e~tcor~ragerr~enl.

it grves me great pleasure nnd satisfaction to &end

my deep sense

of gratitude to my husband, Mr. R. Rajendrurl Nuir, for his patience and

encorr ragerr lent ex-tended to n2e dl these years.

1 urlsh to express my indebtedness to ttly cluldren Master Deepak K.

Nair and Muster Aravind R. Nuir, who tolerated all the inconveniences and difficulties during the course of this research work
1 express my gratitude lo mj sisters for their moral support and

encouragemerzt througkwut m y research programnte.

I ~ . r p r e s . smu t h a n k to all those who have directly or indirectly

IzeJped me ui con~pleting thts resecwch work

Above ali I Il~rrrtk Gvri fur- file bIessings showed or)
sucr:essfili cornpletiorz of this work.
r 7 1 ~

for Ihp

Meenakumury S ,

NOTATIONS AND ABBREVIATIONS

suc mal ox bipy phen py pn en M ml mM n N r R S g() eff f() T Ti Tf Ts log succinate dianion malonate dianion oxalate dianion 2,2'-bipyridyl 1,10-phenanthroline pyridine 1,3-diaminopropane ethylenediamine metal millilitre millimole order parameter normality correlation coefficient fraction decomposed gas constant, resistance linear rate of a TG reaction change in entropy conversion function effective magnetic moment conversion integral temperature initial temperature final temperature temperature of maximum rate of mass loss. Logarithm to the base 10

ln A tpa D DSC DTG e Ea EPR IR F g h H k

natural logarithm frequency pre-exponential factor terephthalate dianion diamagnetic correction differential scanning calorimeter derivative thermogravimetry base of natural logarithm energy of activation election paramagnetic resonance infrared triply degenerate gram plancks constant change in enthalpy boltzmann constant

CONTENTS
CHAPTER 1 Introduction 1.1 1.2 1.3 1.4 1.5 1.6 Monocarboxylates : Structure and Bonding ......................... 2 Dicarboxylates : Structure and Bonding .............................. 9 Carboxyl Group in Biology ................................................ 24 Metal Carboxylates as Synthetic Model Complexes ............ 30 Metal Carboxylates in Catalysis ........................................ 31 Scope and Objectives ........................................................ 33 References ........................................................................ 37 CHAPTER 2 Reagents and Physico-Chemical Methods 2.1 2.2 2.3 Reagents........................................................................... 51 Preparative Details ........................................................... 51
2.2.1 Metal dicarboxylates .................................................... 51

Elemental Analysis ........................................................... 52

2.3.1 Estimation of nickel ..................................................... 52 2.3.2 Estimation of cobalt .................................................... 52 2.3.3 Estimation of copper .................................................... 53 2.3.4 Estimation of carbon, hydrogen and nitrogen .................. 53

2.4

Spectral Methods .............................................................. 53

2.4.1 IR spectra .................................................................. 53 2.4.2 Electronic spectra ....................................................... 53 2.4.3 EPR spectra .............................................................. 54

2.5 2.6 2.7 2.8

Coordination Chemistry of Copper(II) ................................ 58 Coordination Chemistry of Cobalt(II) ................................. 60 Coordination Chemistry of Nickel(II) .................................. 62 Thermal Analysis .............................................................. 66
2.8.1 Thermogravimetry ...................................................... 66 2.8.2 Differential thermal analysis ......................................... 67

2.9

Magnetic Susceptibility Measurements ............................. 72 References ........................................................................ 74

CHAPTER 3 Interaction of Lewis-bases with Polymeric Metal(II) Succinates 3.1 3.2 Introduction ..................................................................... 78 Experimental .................................................................... 80
3.2.1 3.2.2 3.2.3 3.2.4 3.2.5 3.2.6 Reagents used .......................................................... 80 Preparation of metal(II) succinates............................... 80 Preparation of Lewis-base adducts of nickel(II) succinate .................................................... 82 Preparation of Lewis-base adducts of cobalt(II) succinate ................................................ 83 Preparation of Lewis-base adducts of copper(II) succinate ................................................... 85 Analytical methods ................................................... 87

3.3

Results and Discussion..................................................... 88

3.3.1 3.3.2 3.3.3 3.3.4 3.3.5 3.3.6 3.3.7 3.3.8 3.3.9 Metal succinates of Ni(II), Co(II) and Cu(II) .................... 88 Lewis-base mediated fragmentation of polymeric nickel(II) succinate ...................................... 94 IR spectra ............................................................ 100 Electronic spectra and magnetic data ....................... 105 Lewis-base mediated fragmentation of polymeric cobalt(II) succinate ................................... 110 IR spectra .............................................................. 111 Electronic spectra and magnetic data ........................ 114 Lewis-base mediated fragmentation of polymeric copper(II) succinate................................... 116 IR spectra .............................................................. 117 3.3.10 Electronic spectra and magnetic data ........................ 121 3.3.11 EPR spectra ..................................................... 125 3.3.12 Crystal and molecular structure ............................ 131

References ...................................................................... 140

CHAPTER 4 Thermal Dissociation Features of Sucinate Complexes of Ni(II), Co(II) and Cu(II) and their Lewis-base Adducts 4.1 4.2 Introduction ................................................................... 147 Results and Discussion................................................... 150
4.2.1 Phenomenological aspects ........................................ 151 4.2.1.1 4.2.1.2 4.2.1.3 4.2.1.4 4.2.1.5 4.2.1.6 4.2.1.7 4.2.2 4.2.3 4.2.4 Succinic acid.......................................... 151 Nickel(II) succinate .................................. 151 Lewis-base adducts of nickel(II) succinate... 153 Cobalt(II) succinate ................................. 162 Lewis-base adducts of cobalt(II) succinate .. 164 Copper(II) succinate ................................ 170 Lewis-base adducts of copper(II) succinate.. 172

Kinetic aspects ....................................................... 184 Mechanistic aspects ................................................ 191 Trend in thermal behaviour ...........................................205

References ...................................................................... 209 CHAPTER 5 Interaction of Lewis-bases with Polymeric Metal(II) Malonates 5.1 5.2 Introduction ................................................................... 211 Experimental .................................................................. 213
5.2.1 5.2.2 5.2.3 5.2.4 Preparation of metal(II) malonates ............................. 213 Preparation of Lewis-base adducts of nickel(II) malonate ............................................... 214 Preparation of Lewis-base adducts of cobalt(II) malonate .................................................. 216 Preparation of Lewis-base adducts of copper(II) malonate ................................................. 217

5.3

Results and Discussion................................................... 219

5.3.1 Metal malonates of Ni(II), Co(II) and Cu(II) .................. 219

5.3.2 5.3.3 5.3.4 5.3.5 5.3.6 5.3.7 5.3.8 5.3.9

Lewis-base mediated fragmentation of polymeric nickel(II) malonate .................................................. 223 IR spectra ............................................................ 228 Electronic spectra and magnetic data ........................ 230 Lewis-base mediated fragmentation of polymeric cobalt(II) malonate .................................... 233 IR spectra .............................................................. 233 Electronic spectra and magnetic data ........................ 235 Lewis-base mediated fragmentation of copper(II) malonate ................................................. 238 IR spectra ............................................................. 238

5.3.10 Electronic spectra and magnetic data ......................... 241 5.3.11 Crystal and molecular structure ................................ 244 5.3.12 EPR spectra ............................................................ 248

References ............................................................................ 252 CHAPTER 6 Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) and their Lewis-base Adducts 6.1 6.2 Introduction ................................................................... 257 Results and Discussion................................................... 258
6.2.1 Phenomenological aspects ........................................ 258 6.2.1.1 6.2.1.2 6.2.1.3 6.2.1.4 6.2.1.5 6.2.1.6 6.2.2 6.2.3 6.2.4 Nickel(II) malonate ..................................... 258 Lewis-base adducts of nickel(II) malonate ...... 260 Cobalt(II) malonate .................................... 267 Lewis-base adducts of cobalt(II) malonate ...... 269 Copper(II) malonate ................................... 276 Lewis-base adducts of copper(II) malonate ..... 278

Kinetic aspects ....................................................... 288 Mechanistic aspects ................................................ 291 Trend in thermal behaviour ...................................... 306

References ...................................................................... 309

CHAPTER 7 Interaction of Lewis-bases with Polymeric Metal(II) Oxalates 7.1 7.2 Introduction Experimental
7.2.1 7.2.2 7.2.3 7.2.4

............................................................ 311 ............................................................ 314

Preparation of metal(II) oxalates ................................ 314 Preparation of Lewis-base adducts of nickel(II) oxalate . 316 Preparation of Lewis-base adducts of cobalt(II) oxalate...317 Preparation of Lewis-base adducts of copper(II) oxalate 318 Metal oxalates of Ni(II), Co(II) and Cu(II) ..................... 320 Interaction of Lewis-bases with polymeric nickel(II) oxalate .323 IR spectra ............................................................ 328 Electronic spectra and magnetic data ....................... 331 Interaction of Lewis-bases with polymeric cobalt(II) oxalate .335 IR spectra ............................................................ 335 Electronic spectra and magnetic data ........................ 338 Interaction of Lewis-bases with polymeric copper(II) oxalate 340 IR spectra ............................................................ 340

7.3

Results and Discussion................................................... 320

7.3.1 7.3.2 7.3.3 7.3.4 7.3.5 7.3.6 7.3.7 7.3.8 7.3.9

7.3.10 Electronic spectra and magnetic data ........................ 343 7.3.11 EPR spectra .......................................................... 346

References ............................................................ 348 CHAPTER 8 Thermal Dissociation Features of Oxalate Complexes of Ni(II), Co(II) and Cu(II) and their Lewis-base Adducts 8.1 8.2 Introduction ................................................................... 353 Results and Discussion................................................... 354
8.2.1 Phenomenological aspects .......................................... 355 8.2.1.1 Nickel(II) oxalate .......................................... 355 8.2.1.2 Lewis-base adducts of nickel(II) oxalate ........... 357 8.2.1.3 Cobalt(II) oxalate .......................................... 365 8.2.1.4 Lewis-base adducts of cobalt(II) oxalate ........... 366

8.2.1.5 Copper(II) oxalate ......................................... 373 8.2.1.6 Lewis-base adducts of copper(II) oxalate .......... 374 8.2.2 8.2.3 Kinetic and Mechanistic aspects ............................... 380 Trend in thermal behaviour ...................................... 396

References ...................................................................... 398 CHAPTER 9 Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates 9.1 9.2 Introduction ................................................................... 401 Experimental .................................................................. 404
9.2.1 9.2.2 9.2.3 Reagents used ....................................................... 404 Terephthalate complexes of copper(II) and nickel(II) ..... 404 Lewis-base adducts of copper(II) and nickel(II) terephthalate ......................................................... 405

9.3

Results and Discussion................................................... 407

9.3.1 9.3.2 Metal terephthalates of Cu(II) and Ni(II) ...................... 407 Lewis-base mediated fragmentation of polymeric copper(II) terephthalate ............................................ 409 9.3.3 IR spectra ................................................................ 413 9.3.4 Electronic spectra and magnetic data ........................... 416 9.3.5 EPR spectra .............................................................. 419 9.3.6 Thermal decomposition features ................................. 422 9.3.6.1 Phenomenological aspects ............................. 422 9.3.6.2 Kinetic and mechanistic aspects ..................... 432

References .................................................................... 441 CHAPTER 10 Summary and Conclusion

................................................. 445

Chapter 1 Introduction

nvestigations of novel inorganic-organic hybrid framework assemblies constitute one of the most active areas of materials science and chemical research. The intense interest in these
(1),

materials is driven to a large extent by their unique properties and potential in various applications relating to electrical conductivity photomechanism(3), host-guest chemistry(4), ion

magnetism(2),

exchange, shape specificity and catalysis(5,6), high-temperature and flame resistant fibrous materials(7). Framework materials involving coordination metal complexes constitute major systems which are being probed and developed in the above contexts. Several of these metal-based compounds with low dimensional structures have long been investigated as materials with unusual properties. Molecularbased ferromagnets, conductors and non-linear optical materials represent several applications of such low dimensional coordination polymers.(8-17) The search for molecular building blocks in the design of new extended supramolecular architectures, with tailored electronic or catalytic properties, is a current interest in inorganic chemistry. The synthetic effort is directed mainly toward the preparation of molecular based magnets(18,19) and of inorganic materials with inner cavities and channels mimicking zeolites.(20-23) A successful strategy leading to heteropolynuclear one-, two- and three-dimensional systems is the use of metal cations to link relatively stable coordination compounds containing potential bridging units.

Chapter 1

Among the most oxidised forms of carbon which include

2 and COOH, the carboxyl moiety provides key CO 2 , CO 3

functional manifestations in chemical reactions, biological functions and also in modulating structural, electronic, magnetic and other material properties in systems containing the group. Carboxylic acids, besides being essential building blocks of many life molecules, are very useful functionality in generating hybrid framework materials by interacting with metal ions. The abilities of its anion to coordinate to metal ions in diverse and unique linking modes and switch its ligation characteristics with comparative ease towards metal ions depending on the reaction conditions and available molecular environments have made the carboxylate function versatile structure directing moiety.(24-27) Owing to these reasons, the structural aspects of metal carboxylates have been well investigated. As evident, dicarboxylate compounds can generate a wide variety of polymeric metal complexes with diverse structural features because of their bifunctional nature and easily tunable coordination characteristics. While the main focus of the thesis is the generation and characterisations of interesting structural entities from polymeric metal dicarboxylates we feel it is worthwhile to discuss some of the interesting aspects of metal carboxylates in general. 1.1

Monocarboxylates: Structure and Bonding

Monocarboxylates(24) by themselves are an attractive class of

ligands for the coordination chemists. These versatile moieties bind to metal atoms in a variety of ways giving, in many instances, complexes with interesting structural manifestations and novel electronic, magnetic and other material properties which are also

Introduction

easily accessible. Scheme I shows some of the known modes of coordination of monocarboxylate anions. Unidentate (A) and symmetrical chelate coordination (B) modes are often found and well established, with the unidentate mode being more commonly observed. The presence of unidentate carboxylate can be comparatively easily established through IR spectra, by virtue of the inequivalence of the two C-O bonds in the coordinated anion. However, care must be exercised since the environment of the free carboxylate O atom (and even sample preparation) can influence their IR spectrum.(28-29)

R M O C A R C O M O O B C R M O O C C R O M

R C

M D Syn-syn R

O M

O M M O

R C O M M O

R C O O

E Syn-syn

F Anti-anti

M G Anti-syn

M M H Monoatomic

Scheme 1: Some coordination modes of monocarboxylate anions

The most common bridging mode of coordination is syn-syn (E). The nature of metal-metal interactions as shown in (D) in such systems has been the subject of much study, with interaction varying from the relatively weak in dimeric Cu(II) complexes, to strongly M-M bonded species such as Mo2(O2CR)4 which contain a formal quadruple bond. The two systems which have been most

Chapter 1

studied are the bimetallic (I) and trimetallic (II) complexes, often referred to as paddle-wheel and triangular complexes, respectively.(30)

II

Metal acetates and trifluoroacetates of weak Lewis acids are usually symmetric while those of very strong Lewis acids are often asymmetric.(31) The other forms are not common, but anti-anti single bridging occurs in [Mnsal2enCO2Me]n and anti-syn in [Ph(CH2)3SnO2CMe]n. Trifluoroacetates are known only in unidentate and bridging forms. The syn-syn bridging RCO 2 ligand is extremely common and important in compounds with M-M quadruple bonds. In ionic acetates or acetates in aqueous solution, the free CH3 CO ion has symmetric and antisymmetric C-O stretching 2 modes at ~ 1415 and ~ 1570 cm-1 respectively. These frequencies can vary by 20 cm-1 depending on the system. Since the symmetry of even the free ion is low and gives two IR active bands, evidence for the mode of coordination must be derived from the positions rather than the number of bands. When the carboxyl group is unidentate, one of the C-O bonds should have enhanced double-bond character

Introduction

and should give rise to a high-frequency band. Such bands are observed in the 1590 to 1650 cm-1 region and are considered to be diagnostic of unidentate coordination.(29,32) Symmetrical bidentate coordination as in Zn(CH3COO)2.2H2O and Na[UO2(CH3CO2)3] and symmetrical bridging, as in the M2(O2CCH3)4L2 and M3O(O2CCH3)6L3 types of molecules, leave the C-O bonds still equivalent; but the effect on the frequencies is not easily predictable. In general, multiple bands appear between 1400 and 1550 cm-1, the multiplicity being attributable to coupling between CH3CO2 groups bonded to the same metal atom. The only significant reaction of the carboxylate ligand is decarboxylation, which is often catalysed by transition metal species.(33) Straight-chain alkyl carboxylic acids derived from petroleum and which also have a terminal cyclohexyl or cyclopentyl groups are known as naphthenic acids. They form complexes, presumably polymeric, with many transition metals, and are freely soluble in petroleum. There are, of course, more complicated carboxylic acids such as ethylenediaminetetraacetic acid that can function as multidentate ligands with both N and O bound to the metal. Also hydroxo carboxylic acids such as citric acid readily form complexes in which both carboxylate and hydroxo groups are involved in co-ordination. Among these, probably the best studied are tartrato complexes.(34) A fairly common type of structure is one in which it bridges two metal atoms. A particular example is in the case of antimony complex which is known as tartar emetic (III).

Chapter 1

III Because of the chirality and multiplicity of bonding possibilities, many isomers of tartrate complexes are possible, and the relative stabilities of these can be explained in terms of steric constraints of the binuclear structure and conformation of the tartrato groups, and depend strongly on the coordination geometry around the metal. Oxygen centred triangles(35) are important units found widely in so- called "basic" carboxylates and a few other bridging anions of many transition metals like V, Cr, Mn, Fe, Co, Ru, Rh, Ir and Pt. For the +3 state they have the general formula (M3O(OOCR)6L3]+ where L is a ligand such as H2O or pyridine and it has general structure as in IV.

IV

Introduction

Metal

carboxylates,

in

general,

are

known

to

take

multivarious structures.(36-38) The acetate of Cu(I) is obtained as white air-sensitive crystals by reduction of Cu(II) acetate by Cu in pyridine or MeCN and has a planar chain structure (V). By contrast the trifluoroacetate (CuO2CCF3]4.2C6H6, and benzoate (CuO2CPh)4 complexes are tetramers with bridging carboxylates as in VI. However, this is the only one type of Cu4 polynuclear structure known.

V carboxylates are

VI

Compared to the Cu(I) species mentioned above, copper(II) known to be binuclear with four carboxylate bridges and may additionally have end groups as in VII

VII

Chapter 1

Polymeric species are known to be formed by interaction of

II tetrahydrothiophen (L) and CuCl2, which gives [Cu 1 3 Cu LCl5]n species

while

the

action

of

P(OMe)3

on

copper(II)

carboxylates

gives

Cu3(O2CR)5[P(OMe)3]2 that may have units linked as in VIII.(39)

VIII Oxo-centred complexes can have 4-tetrahedral oxygen in the center of a tetrahedron of divalent metal atoms as in M4O(O2CMe)6 or in similar clusters. The best known complex is Be4O(O2CMe)4. Similarly ZnII and CoIV analogues are also known.(40) The manganic acetate is actually an oxo-centred species, [Mn3O(O2CMe)6]CO2Me. Interaction of the acetate with bipy in MeCN gives Mn4O2(O2CMe)7(bipy)2, which is considered as a model for the Mn complex involved in photosynthesis.(41) One of the earliest CrII compounds it is red discovered and (1844) was the the acetate hydrate, CrII This Cr2(O2CCH3)4(H2O)2. It was long recognized as anomalous because diamagnetic, whereas mononuclear compounds are blue or violet and strongly paramagnetic. Cr2(O2CR)4 L2, have the type of structure shown in IX.

compound as well as numerous others of the general formula

Introduction

IX It is now well understood that the chromium atoms are united by a quadruple bond in this dimer but the strength of this interaction is sensitive and depends as inverse function of the bonding strength of the axial ligand. It is also sensitive to the basicity of the RCO 2 groups. 1.2

Dicarboxylates: Structure and Bonding

Dicarboxylic acids are more complex than the corresponding

monocarboxylic acid in transition metal coordination chemistry due to varied coordination behaviour in the resulting complexes.(42-45) Dicarboxylic acids being bifunctional molecules can bind metal ions through both of their carboxylate functions and can lead to extended polymeric systems. Besides the ability to exhibit diverse linking characteristics through COO groups resulting in highly tunable structural features, the nature of the spacer moiety between the two carboxylate functions can also contribute substantially to the structural architecture of the resulting framework materials. Dicarboxylic acids, as chelating ligands, control the oxidation state of transition metal and builds the skeleton of inorganic framework both as a part of the oxide sheet and pillars between layers. The three

10

Chapter 1

dimensional framework of transition metal carboxylate opens a new series of transition metal complexes for engineering tailored materials. Hybrid inorganic-organic compounds are attracting interest as a class of materials that are well suited for the incorporation of transition metals into porous frameworks.(46-48) In such materials, functionality can be introduced from either the inorganic species or the organic linker molecules. Transition metals are well known to confer redox character to zeolite hosts and may impart interesting magnetic and spectroscopic properties to porous materials. Organic species, on the other hand, can be used to adjust the channel size, after the surface of pores and impart chemical reactivity or chirality. For transition metal carboxylates, several examples of multidimensional metaloxygen connectivity occur for materials made with linear dicarboxylic acids. Many researchers were interested in the use of the complexing properties of carboxylic acid to build open structure materials.(49,50) In other words dicarboxylate ligands could be fruitfully used to obtain extended solids with open frameworks.(51-54) The simplest and most intensively studied among these dicarboxylic acids is oxalic acid (ethanedioic acid), which has no spacer entity between the two -COOH groups. Several coordination modes for this acid are possible and these are represented in Scheme 2. Unlike monocarboxylates, chelate coordination is favoured for oxalates over the unidentate mode. Of the two modes of chelate coordination, the formation of the larger chelate ring (D) is generally formed in preference to the four-membered chelate ring (C), with the latter becoming more common in higher members of the dicarboxylate series, where the two carboxylate groups are farther apart.

Introduction

11

Scheme 2: Some coordination modes of oxalate dianion

There are many possible bridging modes for this simplest dicarboxylic acid and among these, the tetradentate bridging mode (F) is the most common. X-ray diffraction is the most reliable method of determining the coordination mode of the dicarboxylates, although chemical methods have been somewhat useful. For example, protonation reactions can reveal the presence of uncoordinated carboxylate groups, since these are easily protonated unlike the coordinated groups. Metal interactions in dicarboxylate complexes, particularly oxalate complexes, have been of interest, with copper complexes being the most studied. The magnetic properties of oxalatebridged CuII dimers [LCu(ox)CuL]2+ have been found to be highly variable, and strongly influenced by the nature of the terminal ligands L and L'.(55) Dicarboxylate complexes are usually synthesized by reaction of an aqueous solution of the alkali metal salt of the dicarboxylate with a metal halide, or by reduction of a metal salt by the dicarboxylic acid. For example, oxalic acid readily reduces iron oxides to form the iron(II) complex.

12

Chapter 1

The oxalate ion has been known to function as a bis-bidentate ligand and its coordination to two metal ions affords a wide variety of polynuclear compounds.(56-59) There are four types of polymerisation A-D, which are shown in Scheme 3.

Scheme 3: Types of polymerisation in oxalate ion

As in A linear chain structures are formed, in which the bridging oxalate ions coordinate in a monodentate fashion.(60,61) In B each copper ion has a square-planar coordination geometry having bis-bidentate oxalate with adjacent, copper ions bridged by

Introduction

13

a single oxalate ion.(58,59,62)

The extended linear chain systems

having bis-bidentate oxalate (C and D) are intriguing, concerning their magnetic behaviour, thermal and solid state reactions. Recently, compounds of the type C have been synthesised, whereas no single X-ray crystal structure of D has been reported in spite of its importance. The occurrence of long range magnetic order in lattices composed of molecular transition metal complexes has been attracting increasing attention in recent years.(63) Such compounds are of interest because they are insulating and frequently transparent and offer the opportunity of creating novel lattice architectures. They also offer the chemist the opportunity to investigate how magnetic exchange interactions are propagated through extended and conjugatively connected polyatomic ligands. Prominent among the latter is the ambidentate oxalate ion. Numerous dimeric and trimeric oxalate complexes have been prepared as models exhibiting novel properties. (64,65) Exchange coupled clusters of transition metal ions are relevant to many different scientific areas ranging from chemistry to solid-state physics and to biology.(66-68) There is active interest from the bio-inorganic community in heterometal polynuclear complexes because an increasing number of active centres in metalloproteins are found to contain more than one metal atom. The oxalato group has shown to be an excellent bridging ligand to achieve a strong antiferromagnetic interaction between metal ions far away from each other in homobimetallic complexes.(55,69) Polynuclear metal complexes are of considerable current interest in relation to the nature of magnetic exchange interaction between metal

14

Chapter 1

ions through bridging ligands(70-73) and as models for the active sites of metalloenzymes.(74-76) hemocyanin, Many of these etc.(77-80) compounds are prepared in oxalato bridged metal attempts to mimic the behaviour of various dicopper proteins such as tyrosinase Various complexes have structures like honey-comb layer
(64,65,81)

(X), chicken

wire sheet (82,83) (XI-XII) and enantiomeric chains (83) as shown in XIII.

XI

XII

XIII

In the field of molecular based magnetism structurally two dimensional attracted (2D) bimetallic interest oxalate in bridged networks Since have the increasing recent years.(84)

ambidentate oxalate ions act as mediators for magnetic exchange

Introduction

15

interactions between the transitionmetal centres, short range and long range magnetic ordering behaviour may occur, and consequently, from this molecular class of compounds emerge materials with distinct magnetic properties. The role of dipositive tris-chelated transition metal bipyridine complexes as templates in the formation and crystallization of chiral, three dimensional (3D) homo and bimetallic oxalate bridged networks is now well established.(85) The topological, chemical and physical properties of the resulting polymeric frameworks are fascinating. The oxalate ion is an efficient bridging ligand for the stepwise synthesis of homo and hetero-polynuclear complexes. This ion is known to be one of the few ligands for which systematic photochemical information regarding various metal ions exists.(86,87) Oxidation-reduction is the principal photochemical reaction whereby in the complexes of tripositive metal ions, the metal ion is reduced from the trivalent to the divalent state and the oxalate ligand is finally oxidized to CO2. In addition to its reducing property, the oxalate ion is a versatile ligand since it can act as a mono, bi, tri and tetradentate ligand capable of forming bridged polynuclear complexes.(88) Self assembly of metal compounds by hydrogen bonds into one-, two- and three-dimensional supramolecular architectures, encompass biological and material areas and provide an opportunity to consider them in unison.(89-91) Many oxalato bridged complexes have in fact very interesting 1D,(92-94) 2D framework structures
(97-101) (95,96)

(XIV) and 3D

(XV) and associated properties.

16

Chapter 1

XIV

XV

The coordination features of malonic acid which has a -CH2linker between the two -COOH groups is of current interest due to the versatile binding modes of its dianion (eg: syn-syn, syn-anti, anti-anti and monoatomic) which can simultaneously function as bidentate chelate as well as bridging ligand through the carboxylate groups to neighbour metal ions, which can propagate the electron transfer between paramagnetic centres leading to specially interesting magnetic materials.(24-26,29) Magnetic studies on the carboxylate bridged compounds generally indicate that syn-anti mode induces ferromagnetic interactions where as anti-anti and syn-syn induce antiferromagnetic interactions. Several examples of metal complexes of malonate and bimalonate having polymeric,(102-105) helical(106) and 3D network are known of which a representative structure is given in XVI.
(107,108)

Introduction

17

XVI In addition to this, numerous layer-type polymeric malonato complexes have also been reported (XVII).(109) These layers, which contain infinite puckered four-membered M-O-M-O rings in a pseudo-ternary symmetry, are formed by the metal and one independent malonate group. They are interconnected by the second independent malonate group, giving a three-dimensional framework. In this one malonate group is monodentate and triply bridging and chelating, whilst the other is doubly monodentate. The extensive network of hydrogen bonds and bridge bonds observed in this structure enhances the structure stability.

18

Chapter 1

XVII It is worthy to note that metal malonate and several of its analogue complexes are seen to have promising anti-tumor properties.(110) Succinate ions with -CH2-CH2- spacer between the two carboxylate functions are known to employ two distal carboxyl O atoms to link transition metal atoms into 1D polymeric or supramolecular chains.(111-114) Previous investigations show that ,-dicarboxylate anions are interesting flexible bridging ligands to interlink metal atoms into supramolecular architectures with specific topologies.(115-118) In addition, the succinato ligands polydentately link metal atoms to form 2D and 3D networks.(119,120) By adopting the hydrothermal techniques various metal succinates with 1D(121)(XVIII), 2D(122-126)(XIX, XX) and 3D(121,127) (XXI, XXII) framework structures have been prepared. Under hydrothermal conditions, the temperature favours inorganic condensation (decrease of water polarity, modification of equilibrium constants). The condensation is therefore perturbed by the presence of the coordinated organic ligand. Under mild conditions, the stabilization of infinite networks comes from the bifunctional character of the

Introduction

19

ligands, which can bridge metal centres. The suggested honeycomb structure(128) of nickel succinate with hydroxyl group contains layers of edge-sharing NiO6 octahedra connected by isolated corner sharing NiO6 octahedra (XXIII). It may be considered as the first metal carboxylate with fully 3D M-O-M connectivity. The most prominent feature of the nickel succinate structure is the presence of unidimensional pores. The pores are lined almost entirely by the methylene groups of the dicarboxylate, which creates an exceptionally hydrophobic surface.

XVIII

XIX

XX

20

Chapter 1

XXI

XXII

XXIII Benzoic acidbased ligands have led to a variety of structures as these ligands can form short bridges via one carboxylate end or longer bridges through the functionalized benzene ring. Recent reports of terephthalic acid (tpa) bridged coordinate to the Cu(II) centers have shown that the ligand can

metal in either in chelating bis-bidentate(129) (A) or bis-monodentate (B)(129-132) or bridging bis-monodentate (syn-syn) (C)(133) fashion (Scheme 4). The tpa ligand can form multidimensional compounds owing to its multibinding ability with regard to metal ions.(134)

Introduction

21

Scheme 4: Some typical coordination modes for tpa ligand.

Increasing attention has been paid to the construction of two-dimensional (2D) or three-dimensional (3D) magnetic systems in order to gain a better understanding of the correlation between structure and magnetism.(135-137) One strategy to build a spatially well-spanned framework, among others, is to utilize certain features of potentially bridging ligands, such as conformational flexibility, versatile binding modes, and the ability to form hydrogen bonds. The terephthalate ligand can form multidimensional interesting is the current compounds owing to its multi binding ability with regard to metal ions.(134) The design of supramolecular structure with recent years.(138) A rapidly inclusion and magnetic properties has been extensively studied in developing area in this field synthesis of extended inorganic structures where the ability to control functionality along these networks is of much interest.(139) There are several reports of terephthalato bridged complexes having 1D chain (XXIV)(140-150), 2D layered (XXV, XXVI)(140,151) and 3D network structures (XXVII).(152-156)

22

Chapter 1

XXV

XXIV

XXVI

XXVII

In XXIV, tpa has a bridging bis-monodentate binding mode while in XXV, a mono-bidentate binding mode. In XXVI, there are two types of edge sharing MO6 chains that are connected to each other by OH (M-O-M bridges) to form layers that are further joined together through terephthalate ion. Evidently these types of compounds exhibit unusual magnetic properties. It is instructive to discuss in some details the relative magnitude of formation constants of ternary complexes involving dicarboxylate systems. The formation constants of the ternary complexes have been evaluated by a variety of methods
(157,158)

depending upon the nature of the interaction between the metal ion

Introduction

23

and ligands, and the values are given in Table 1.1, along with those of the binary system. Table 1.1- Formation Constants of Ternary Complexes (Malonic Acid (A)-Cu(II)-Ligand(L) Complexes)
Ligand(L) Oxalic acid Succinic acid Maleic acid Fumaric acid Phthalic acid Salicylic acid 2,2'-Bipyridyl Ethylenediamine log K ML 4.28 3.23 4.02 3.19 3.49 10.83 8.00 10.31
M

log K ML 2 3.97 2.82 2.59 8.05 5.60 8.60

ML

log MAL 8.54 8.16 9.39 6.28 9.16 16.40 14.61 15.30

log K -0.57 0.10 0.54 -1.74 0.84 0.74 1.78 0.16

log X 0.72 3.83 4.13 5.81 7.51 3.58

The stability constants of ternary complexes are characterized by the difference in stability constants ( log K) which is given by eq (1.1), and the disproportionation constant (log X) which is given by eq (1.3), the equilibrium being represented by eq (1.2).
M log K = (log K MA MAL log K ML )

ML M = log K MLA log K MA

..(1.1)

MA2 + ML2

2MAL;

24

Chapter 1

X=

[MAL]2 [MA 2 ][ML 2 ]

..(1.2)

logX = 2 log MAL-(log MA 2 +log ML 2 )

(1.3)

The values expected for logK and logX, from statistical arguments(159) are 0.3 to 0.9 and 0.6, respectively. Higher values of logK and log X indicate that the ternary complex formation is favoured over the binary ones. The data presented in Table 1.1 show that the experimental logK and log X values are greater than the statistical ones, indicating that apart from the statistical factors the stability of the ternary complexes is also governed by other factors like ring size of chelate, neutralization of charge in the ternary complex formation and formation of -bonds. 1.3 Carboxyl group in Biology As mentioned earlier the -COOH groups are essential functionality of a variety of life molecules starting from amino acids. The group provides high compatibility for -NH2 function to form zwitter ions in terms of matching acid-base strengths. Among several metalloenzymes it is noteworthy to mention some aspects about 'Carboxy peptidase A' (CPA). It is a type of enzyme, with a molecular weight of ~ 34, 600 which catalyzes the hydrolysis of the terminal peptide bond at the carboxyl end of proteins and other peptide chains. It is also effective toward correspondingly placed ester linkages. There is a marked preference for peptide bonds in which the side chain of the terminal residue is aromatic or a branched aliphatic chain. CPAs

Introduction

25

have been found in the pancreas of many mammals including man. The carbonyl oxygen atoms of the peptide or ester link that is to undergo hydrolysis are coordinated to the Zn atom. polarizes it in the strong

This

O C + sense, thus making the C atom more

linkage (XXVIII) to the terminal

prone to nucleophilic attack. The arginine -145 residue forms a hydrogen-bonded carboxyl group. This accounts for the specificity of the enzyme for catalyzing hydrolysis of the terminal residue at the carboxyl end of a peptide. It also results in a good fit of a large non-polar side chain on the terminal residue into an available hydrophobic pocket. At this point, the so-called Michaelis complex is in fact formed. Beyond this, there has been considerable controversy as to how bond scission and generation of products is actually accomplished (Scheme 5).

H O H N C C O H N H

H C N

XXVIII

26

Chapter 1

Scheme 5 : A possible mechanism for the action of carboxypeptidase, X represents either O or NH, and the steps are not all written so as to be balanced with respect to protons A key point in favour of this scheme is that it can account for the accepted fact that following the Michaelis complex, another metastable complex (or intermediate) is formed, and only then is the product complex formed, from which the products, RCO 2 + HOCR HCO 2 or

RCO 2

+ H3NCR HCO 2 , promptly dissociate,

Introduction

27

leaving the enzyme ready for the next cycle. This second complex must be one of the species in which there is an intermediate anhydride involving the carboxyl group of Glu-270. It is to be noted that another key step in the mechanism is the generation of a ZnOH group, which is responsible directly for the attack on the carbonyl carbon atom. The zinc ion thus serves twice as a Lewis acid: once in binding and polarizing the carbonyl group and again in enhancing the acidity of the bound water molecule so that it can become the necessary OH nucleophile. There is indirect evidence for the occurrence of this Zn-OH attack on the mixed anhydride intermediate from study of model systems.(160) The naturally occurring polymeric carboxylic acid derivatives of vital biochemical importance are proteins (polyamino acids), polysaccharides (polycarbonates) and nucleic acids, (polynucleotides). Prostaglandins are naturally occurring carboxylic acids that are widely distributed in mammalian tissue. They play a vital role in many biological processes, including blood platelet aggregation (clotting), the regulation of blood pressure, the pain response and fertility control. The prostaglandins are all C20 compounds related to eicosanoic acids or prostanoic acid in structure.(161,163,164)
9 10 14 7 8 6 5 4 16 15 17 3 2 18 1

COOH
20 19

COOH

11

12 13

CH3

eicosanoic acid

prostanoic acid

28

Chapter 1

Carboxyl group finds wide applications in biomedical and other related industries. Dacron, an important polyester formed from diethyl terephthalate and ethylene glycol(161), is of exceptional strength and is widely used to make fabrics and film backing for recording tapes.(162) Dacron fabrics have been used to repair or replace segments to blood vessels and heart valves. The parabensesters of p-hydroxy benzoic acids are used to inhibit moulds and yeast in cosmetics, pharmaceuticals and food.(162) Various types of esters are used in the food and perfume industries as flavour and for fragrance compounds.(161) Some are referred below.
O O H C OCH2CH3 CH3 O C O(CH2)7CH3 C OCH3 OH

ethyl formate (rum)

octyl acetate (oranges)

methyl salicylate (oil of wintergreen)

Olestra, ester of sucrose with fatty acids, is a nutritional novelty, a product that tastes like a cooking oil but that adds no calories to the diet.(165-167) Metal naphthenates such as copper naphthenates are used as fungicides; aluminium naphthenates are used as a gelling agent in napalm and cobalt naphthenates find use in paints. Dilute solution of acetic acid is used as vinegar. Acetate ion is major intermediate in the metabolism of carbohydrate, lipids and proteins. Calcium and sodium salt of propanoic and sorbic acids are used in baked foods and processed cheese. They are also present in fruit juices, wines, soft drinks etc. Sodium benzoate is used as ingredient for beverages, syrups, pickles, fruit salads

Introduction

29

etc.(162) Many of the insect pheromones are carboxylic acids or their derivatives.(161) The interesting examples are given below.
O

CH3 CH3

CH3(CH2)3 C H C

(CH2)5CH2O C H

CH3

CH CH2 CH2 O C CH3

isoamyl acetate (honey bee alarm pheromone)

cis-7-Dodecenyl acetate (cabbage looper sex pheromone)

Aspirin (acetyl salicylic acid) is the most widely used drug in the world.(161) It is used as a pain reliever (analgesic), in the reduction of fever (antipyretic) and also as an agent for anticoagulation of blood. Nylon 6,6 an important polyamide, prepared from adipic acid and hexamethylenediamine, is more resistant to combustion and is immune to insect attack. In medicine, nylon is used in specialised tubing and as velour for blood contact surfaces. Nylon sutures were the first synthetic sutures and are still commonly used. High level of the omega-3 fatty acids in marine oils provides protection against diseases. Human milk contains 3-docosahexaenoic acid, which is essential for the retina and brain of infants.(168)

COOH

-3-docosahexaenoic acid

30

Chapter 1

The tartrate complex of antimony(III), K2[Sb2(d-C4O6H2)2] .3H2O, has been known in medicine for over 300 years. It is used for treatment of schistosomiasis and leishmaniasis and its toxic side effects can be mediated by pencilamine. Reports are available on several metal carboxylate complexes which are known to be exhibiting good anti-tumour activities having less toxic effects. (169,170) The important role of the dicarboxylic acids in life systems has long been well recognized by chemists and biologists. A wide range of simple aliphatic acids are ubiquitous in solids and plants viz., oxalic, malonic, malic, tartaric and citric, which are known for their metal-binding roles.(171) Tiffen was the first to identify ironcitrate complex in plant xylem.(172,173) This oxalato chromate(III) a plant species.(174) anion has been found in the leaf tissues of

For animal fluids also Ca2+ and Mg2+ citrate bindings are found. Ascorbic acid plays an important role in human iron metabolismas one of the postulated factors aiding iron uptake. It reduces FeIII to FeII and also reduce CuII to Cu1.(175)

1.4

Metal Carboxylates as Synthetic Model Complexes

The report of a bioactive Cr-nicotinic acid complex sparked a

brief

but

intense acid

interest

in

the

preparation the

of

synthetic

Cr-nicotinic

complexes.

Among

well-characterized

Cr-nicotinic acid complexes, coordination of the ligand via the pyridine N and via the carboxylate oxygens have both been established.(176-178) A Cr-nicotinic acid-gluthathione complex has demonstrated appreciable activity in rat adipocyte assays.(`179)

Introduction

31

Well-characterized chromium-salt anion assemblies bridged by carboxylate ligands are few with the exception of those possessing the basic acetate type structure [Cr3O(O2CR)6L3]+, (L = H2O, py) (XXIX).

XXIX These trinuclear oxo-centered metal carboxylate assemblies have been of intense interest for several decades; these compounds serve as important models to test theories of magnetic coupling between metal ions in multinuclear systems(180) and as precursors to larger multinuclear assemblies whose novel magnetic properties have only recently been realized. Two tetranuclear, carboxylatesupported assemblies have been reported; [Cr4S(OAc)8(H2O)4]2+ and [Cr4O2(OAc)7(bipy)2]+ (182) which have interesting structures. 1.5
(181)

Metal carboxylates in Catalysis

Carboxylates of general formula Rh2(-O2CR)4 are known for

their catalytic reactions such as hydrogenation or cyclopropanation of alkenes. They can act as hydrogenation catalyst in DMF and in presence of phosphenes. Cuprous carboxylate complexes are Another example which considered to be the first complexes involved in homogeneously catalysed hydrogenation reactions.(183,184)

32

Chapter 1

is of synthetical importance is Hurtely reaction, involving the condensation of benzoic acid units with -carbonyls. (185-187)

CO2H + H2C(C R1 ) (C R2) Br O O 2 NaOEt [Cu] kat

_ + CO2 Na
2

CHCOR COR
1

Similarly Lead tetra acetate is known for its strong but selective oxidising property in organic chemistry.(188)
OH OH _ n C4H9 O 2CCH CH CO 2 C4H9 _ n + Pb(OAc) 4

C6H6

2 n _ C4H9O 2CC

O H

di-butyl tartrate

1-butyl 2-oxoethanoate

The ability of some metal dicarboxylate complexes, especially manganese dicarboxylate complexes to act as functional models for the non-haem catalases which have been recently isolated from Lactobacillus plantrum, is known.(189,190) Such biomimetic materials can be used not only to shed light on the chemistry of biological materials but also as catalysts in processes such as low temperature bleaching. The catalytic activity of these species for the disproportion of hydrogen peroxide, a reagent which is important for cell detoxification, has been investigated in detail inorder to establish the mode of action of the natural catalases.(191)

Introduction

33

1.6.

Scope and Objectives

A closer look at the structural aspects of all the known

metal dicarboxylate reveals that there is a major role for any additional ligand in deciding the final structure of the framework. This is evident from the structural details available for mixed ligand complexes of metal dicarboxylates having Lewis-bases as an additional constituent. The reports of such metal complexes often appear as random references and it is seen that their preparation involves combined interaction of metal salts, dicarboxylic acids and Lewis-bases in appropriate conditions. As evident from the synthetic procedure and their compositions these framework materials can be considered to be getting formed by chance rather than by choice or selection. Further, the anions of the metal salt employed are also seen to be complicating the nature of the final products. Therefore a more strategic route to generate varieties of tailored framework materials of mixed ligand complexes of choice could be the interaction of Lewis-bases directly with metal dicarboxylate complexes. The present study is aimed at generating such molecular frameworks having diverse compositions and structural features by systematic study involving the interaction of polymeric metal dicarboxylates with varieties of Lewis-bases in various conditions and stoichiometry. It has also been well demonstrated that dicarboxylate systems with variable intervening spacer moieties when interacted with metal ions yield interesting and novel supramolecular architectures whose features and dimensionality get dictated by the nature of metal ion, spacer function and reaction

34

Chapter 1

conditions.(192,193)

We could generate several new mixed ligand

complexes with varying compositions by Lewis-bases mediated fragmentation of polymeric transition metal dicarboxylate systems. The main focus made in the present study are on the following aspects. 1. The selection of the dicarboxylic acids is made such that they have varying nature of the spacer moiety between the two carboxylate functions. The dicarboxylic acids chosen are succinic acid (H2suc), malonic acid (H2mal), 1,4-benzene dicarboxylic acid (H2tpa) and oxalic acid (H2ox) having -CH2-CH2-, -CH2-, phenylene moieties respectively as spacer group for the first three and no spacer for the oxalic acid. The selection is made such that we get systems with both flexible and rigid functions. The Lewis-bases selected are ethylenediamine (en), 2,2'-bipyridyl (bipy), 1,10-phenanthroline (phen), 1,3-diaminopropane (pn) and pyridine (py) which are either chelating, conjugatively chelating or monodentate in nature so that the systems with diverse structural variations could be generated. We have confined our studies mostly to nickel(II), cobalt(II) and copper(II) ions. 2. Generation of metal succinates by various synthetic routes and their structural characterisation. 3. Systematic investigations on the nature of interaction of various Lewis-bases with the metal succinates developed above and characterisation of the resulting framework materials.

Introduction

35

4.

Attempts to grow single crystals of the above complexes and the crystal as well as the molecular structure determination by X-ray diffraction techniques.

5.

Since there is the possibility of reversible adduct formation with some of the Lewis-bases and metal succinates with the possible structural modification, attempt has also been made to study the thermal decomposition features of the adduct formed in the above cases and also the evaluation of the associated thermodynamic parameters.

6.

Developing various metal malonates and their characterisation by spectral and other analytical measurements.

7.

Investigations on the Lewis-bases mediated fragmentation of the polymeric metal malonates with the various Lewis-bases and detailed structural characterisation of the resulting mixed ligand complexes as generated above.

8.

Attempts to grow single crystal of some of the adducts of metal malonates and their detailed crystal and molecular structure characterisation by XRD technique.

9.

Detailed thermal characterisation of both metal malonates and their various Lewis-base adducts and also the evaluation of the thermodynamic parameters.

10. Generation of metal oxalates by various synthetic routes and their characterisation by spectral and other analytical techniques.

36

Chapter 1

11. Systematic and structural characterisation of the adducts generated by the interaction of various Lewis-bases with various metal oxalates. 12. Detailed investigation on the thermal features of both the metal oxalates as well as their various Lewis-base adducts generated as above. 13. Generation structural of metal terephthalate of complexes products and their

interaction with various Lewis-bases and also the spectral and characterisation the formed. Investigations on the thermal decomposition features of the metal terephthalates and their various Lewis-base adducts are also attempted.

Introduction

37

Reference 1. 2. W. Kobel and M. Hanack, Inorg. Chem; 25 (1986) 103 (a) M. Kubo, Coord. Chem. Rev; 21 (1976) 1 (b) S. Kawata, M. Kondo, I. Furuchi and M. Munakata, Angew. Chem. Int. Ed. Engl; 33 (1994) 1759 3. 4. 5. 6. C. G. Pierpont and O. Jung, J. Am. Chem. Soc; 116 (1994) 2229 Y. Kwon, S. Washizu and K. Ogura, J. Am. Chem. Soc; 116 (1994) 1151 G. Ciani, D.M. Proserpio and A. Sironi, J. Am. Chem. Soc; 117 (1995) 4562 (a) R. Robson, B.F. Abraham, S.R. Batten, R. W. Gable B. F. Hoskins and J. Liu, Supramolecular Architecture; American Chemical Society, Washington, DC, 1992; Chapter 19.

(b) B.F. Huskins and R. Robson, J. Am. Chem. Soc; 112 (1990) 1546 7. 8. 9. 10. 11. D. W. Krevelen, Angew. Makromol. Chem; 22 (1972) 133 C.T. Chen and K.S. Suslick, Coord. Chem. Rev; 128 (1993) 293 O. Kahn, Molecular Magnetism, VCH, New York (1993) J.S. Miller, Extended linear Chain Compounds, Plenum, New York (1982) P. Delhaes and M. Drillon(Eds.), Organic and Inorganic Linear Dimension Crystalline Materials, NATO ASI Series 168, New York, (1989) K. Nakatani, P. Bergeral and E. Codjovi, Inorg. Chem; 30 (1991) 3977

12.

38

Chapter 1

13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28.

O. Schneider and O. Hanack, Angew. Chem. Int. Ed. Engl; 19 (1982) 79 M. Hanck, S. Deger and A. Lange, Coord. Chem. Rev; 83 (1988) 115 M. Hank, A. Gul and L.R. Subramanian, Inorg. Chem; 31 (1992) 1542 R.C. Alferness, Science; 234 (1986) 825 D. Eaton, Science; 253 (1991) 281 H.O. Stumpf and Y. Pei, J. Am. Chem. Soc; 116 (1994) 3866 H. Okawa and J. Latour, J. Am. Chem. Soc; 116 (1994) 11566 B.F. Hoskins, J. Am. Chem. Soc; 112 (1990) 1546 M. Park and K. Kuroda, Angew. Chem. Int. Ed. Engl; 32 (1993) 884 O. Yahi and G. Li, Angew. Chem. Int. Ed. Engl; 34 (1995) 207 S. R. Batten and R. Robson, Angew. Chem. Int. Ed. Engl; 34 (1995) 820 R.C. Mehrotra and R. Bohra, Academic Press, New York. (1983) Metal Carboxylates;

M. Verdaguer, S. Jeannin and O. Kahn, Inorg. Chem; 23 (1984) 4291 E. G. B. Bassis, C. Tsipis and J. Mrozinski, Inorg. Chem; 25 (1986) 3684 L. S. Kramer, A. W. Clauss, L.C. Francesconi and D. W. Hendrickson, Inorg. Chem; 20 (1981) 2070 G. B. Deacon and R. J. Phillips, Inorg. Chim. Acta; 104 (1985) 41

Introduction

39

29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46.

G. B. Deacon and R. J. Phillips, Coord. Chem. Rev; 33 (1980) 227 R.D. Cannon and R. P. White, Prog. Inorg. Chem; 36 (1988) 195 I.D. Brown, J. Chem. Soc. Dalton Trans; (1980) 1118 K. Nakamoto, Infrared & Raman Spectroscopy of Inorganic and Coordination compounds, Wiley, New York, (1978) E. B. Boyer and S. D. Robinson, J. Chem. Soc. Dalton Trans; (1985) 2113 K. Blomquist and E. R. Still, Inorg. Chem; 23 (1984) 3730 C. E. Summer and G. R. Steinmetz, J. Am. Chem. Soc; 107 (1985) 6124 T. P. Lockhart and D. A. Haitko, Polyhedron; 4 (1985) 1745 S. Shibata et al, J. Chem. Soc. Dalton Trans; (1985) 2555 C. Floriane et al, Inorg. Chem; 26 (1987) 236 J. A. Connor et al, J. chem. Soc. Dalton Trans; (1981) 2119 G. C. Donato and K. L. Busch, Inorg. Chem; 25 (1986) 1551 G. Christou et al, Chem. Commun; 236 (1987) 1303 G. R. Willey and T. J. Woodman, Trans. (1998) 435 Met. Chem; 23

S. Takamizawa and W. Mori, Inorg. Chim. Acta; 283 (1998) 268 S. O. Dunham and E. H. Abbott, Inorg. Chim. Acta; 297 (2000) 72 C. Y. Wong and J. D. Woolins, Coord. Chem. Rev; 130 (1994) 243 A. K. Cheetam and G. Ferey, Angew. Chem. Int. Ed. Engl; 111 (1999) 3466

40

Chapter 1

47. 48. 49. 50. 51. 52. 53. 54.

A. K. Cheetam and G. Ferey, Angew. Chem. Int. Ed. Engl; 38 (1999) 3269 T. J. Barton, L. M. Bull and O. M. Yaghi, Chem. Mater; 11 (1999) 2633 C. Livage, M. Nogues, C. Egger and G. Ferey, J. Mater. Chem; 8 (1998) 2743 F. Serpaggi and G. Ferey, J. Mater. Chem; 8 (1998) 2737 M. Molinier, A. K. Powell and P. T. Wood, Angew. Chem. Int. Ed. Engl; 36 (1997) 991 A. G. Orpen and I. D. Williams, Science; 238 (1999) 1148 C. N. R. Rao, S. Natarajan and R. Vaidhyanathan, Angew. Chem. Int. Ed. Engl; 43 (2004) 1466 (a) J. Kim, B. L. Chen, T. M. Reineke, H. L. Li, M. Eddaoudi, D. B. Molar, M. O Keeffe and O. M. Yaghi, J. Am. Chem. Soc; 123 (2001) 8239

(b) N. L. Rosi, M. Eddaoudi, J. Kim, M. O Keeffe and O. M. Yaghi, Angew. Chem. Int. Ed. Engl; 41 (2002) 284 (c) 55. 56. 57. 58. H. L. Li, M. Eddaudi, M. O Keeffe and O. M. Yaghi, Nature; 402 (1999) 276

M. Julve, M. Verdaguer, A. Gleizes, M. P. Levisalles, and O. Kahn, Inorg. Chem; 23 (1984) 3808 W. Fitzgerald, J. Foley, N. Ray and D. Sheahan, J. Chem. Soc. Dalton Trans; (1982) 1117 H. Oshio, U. Nagashima, Inorg. Chem; 31 (1992) 3295 G. D. Munno, M. Julve, F. Nicolo and J. Faus, Angew. Chem. Int. Ed. Engl; 32 (1993) 613

Introduction

41

59. 60. 61. 62. 63. 64. 65. 66. 67. 68. 69. 70.

D. R. Bloomquist, J. J. Hansen and C. P. Landee, Inorg. Chem; 20 (1981) 3308 A. Gleizes, F. Maury and J. Galy, Inorg. Chem; 19 (1980) 2074 J. Garaj, Chem. Commun; (1968) 904 U. Geiser, R. D. Willett and B. L. Ramakrishna, Inorg. Chem; 26 (1987) 3750 O. Kahn, Molecular Magnetism; VCH, New York, (1994) M. Julve, J. Fans and J. Gleizes, J. Am. Chem. Soc; 106 (1984) 8306 O. Kahn and Y. Pei, Inorg. Chem; 28 (1989) 100 O. Kahn, Angew. Chem. Int. Ed. Engl; 97 (1985) 837 E. Sinn, Coord. Chem. Rev; 5 (1970) 313 O. Kahn, Struct. Bonding; 68 (1987) 89 P. J. Hay and R. Hoffmann, J. Am. Chem. Soc; 97 (1975) 4884 R. D. Willet, D. Gatteschi, O. Kahn and D. Reidel, Eds. Magneto-Structural Correlations in Exchange Coupled Systems; The Netherlands, 1985 R. Vicente and X. Solans, J. Chem. Soc. Dalton Trans; (1996) 1835 D. Gatteschi, O. Kahn, J. S. Miller and D. Reidel, Eds. Magnetic Molecular Materials; The Netherlands, (1991) 198 O. Khan, Molecular Magnetism; VCH, New York, (1993) I. Bertini, H. B. Gray, S. J. Lippard and J. S. Valentine, Eds. Bioinorganic Chemistry; University Sciences Books, Mill Valley, CA, (1994)

71. 72. 73. 74.

42

Chapter 1

75. 76. 77. 78. 79. 80. 81.

S. J. Lippard and J. M. Berg, Principles of Bioinorganic Chemistry; University Sciences Books, Mill Valley, CA, (1994) R. H. Holm and E. J. Solomon, Chem. Rev; 96 (1996) 2239 E. J. Solomon, U. M. Sundaram and T. E. Machonkin, Chem. Rev; 96 (1996) 2563 N. Kitajima and Y. M. Oka, Chem.Rev; 94 (1994) 737 K. D. Karlin and Z. Tyeklar, Adv. Inorg. Biochem; 9 (1994) 123 K. D. Karlin, Science; 261 (1993) 701 (a) H. Tamaki, Z. J. Zhong, S. Kida and H. Okawa, J. Am. Chem. Soc; 114 (1992) 6974 (b) Z. J. Zhong, S. Kida and H. Okawa, Chem. Lett; (1990) 87 (c) C. Mathoniere, C. J. Nattal, S. G. Carling and P. Day, Inorg. Chem; 35 (1996) 1201

82. 83. 84. 85. 86. 87. 88. 89.

P. Roman, A. Luque and J. Cano, Inorg. Chem; 35 (1996) 3741 D. Femande, E. Rochon and A. Marius, Inorg. Chem; 35 (1996) 6086 H. Tamaki, S. Kida and H. Okawa, Chem. Lett; (1992) 1975 S. Decurtins and H. R. Ostwald, Inorg. Chem; 32 (1993) 1888 G. B. Porter and J. G. Doering, J. Am. Chem. Soc; 84 (1962) 4027 E. L. Simmons and W. W. Wendlandt, Coord. Chem. Rev; 7 (1971) 11 K. L. Scott and A. G. Sykes, Inorg. Chem; 12 (1973) 655 B. H. Ye, X. M. Chen, G.Q. Xue and L.N. Ji, J. Chem. Soc. Dalton Trans; (1998) 2827

Introduction

43

90. 91. 92. 93. 94. 95. 96. 97. 98. 99. 100. 101. 102. 103.

M. L. Tong, H. K. Lee, X. M. Huang and R. B. Mak, J. Chem. Soc. Dalton Trans; (1999) 3657 Y. B. Dong, M. D. Smith, R. C. Layland and H. C. Loye, Inorg. Chem; 38 (1999) 5027 O. Castillo, A. Luque, F. Lioret and P. Roman, Inorg. Chim. Acta; 324 (2001) 141 H. Z. Kou, D. Z. Liao and G. M. Yang, Polyhedron; 17 (1998) 3193 J. K. Tang, E. Q. Gao, W. M. Bu and G. L. Wang. J. Mole. Struc; 525 (2000) 271 M. C. Munoz, M. Julve, F. Lioret and J. Faus, J. Chem. Soc. Dalton Trans; (1998) 3125 M. Brezeanu, Y. Journaux and W. Linert, Euro. J. Inorg. Chem; (2001) 2061 J. Fan, W. Y. Sun, K. B. Yu and N. Ueyama, Inorg. Chim. Acta; 319 (2001) 240 X. R. Sun, P. Ching, D. Z. Liao and G. L. Wang, Polish J. Chem; 71 (1997) 7 P. A. Prasad, S. Neeraj, S. Natarajan and C. N. R. Rao, Chem. Commun; (2000) 1251 E. Coronado, J. R. G. Mascaros and C. J. G. Garcia, Inorg. Chem; 40 (2001) 113 X. F. Chen, P. Chen, X. Liu, B. Zhao, D. Z. Liao, S. P. Yan and Z. H. Jiang, Inorg. Chem; 40 (2001) 2652 I. G. Filippova, V. K. Kravtsov and M. Gdanec, Russian J. Coord. Chem; 26 (2000) 809 C. R. Perez, M. H. Molina and J. Sanchiz, Inorg. Chim. Acta; 298 (2000) 202

44

Chapter 1

104. 105. 106. 107. 108. 109. 110. 111. 112. 113. 114. 115. 116. 117.

E. V. Brusau, G. E. Narda and J. C. Pedregosa, J. Solid State Chem; 143 (1999) 174 Y. G. Wei, S. W. Zhang, M. C. Shao and C. O. Liu, Polyhedron; 15 (1996) 4303 Y. G. Zhang, J. M. Li and J. H. Chen, Inorg. Chem; 39 (2000) 2330 Y. Rudong and Y. Lan, Polyhedron; 11 (1992) 2051 C. R. Perez, M. H. Molina and J. Sanchiz, Inorg. Chim. Acta; 298 (2000) 245 B. Benmerad and F. Balegroune, Acta Crystallogr; C56 (2000) 321 P. Bitha and G. O. Morton, Inorg. Chem; 29 (1990) 645 M. P. Gupta, R. D. Sahu, R. Ram and P. R. Maulik, Z. Kristallogr. NCS; 163 (1983) 155 Y. Q. Zheng and J. L. Lin, Z. Kristallogr. NCS; 215 (2000) 157 M. Fleck, E. Tillmanns and L. Bohaty, Z. Kristallogr. NCS; 215 (2000) 429 M. Fleck, E. Tillmanns and L. Bohaty, Z. Kristallogr. NCS; 215 (2000) 619 B. H. O Connor and E. N. Maslen, Acta Crystallogr; 20 (1966) 824 Y. Q. Zheng, J. Sun and J. L. Lin, Z. Anorg. Allg. Chem; 626 (2000) 1718 (a) Y. Q. Zheng, J. L. Lin, J. Sun and H. L. Zhang, Z. Kristallogr. NCS; 215 (2000) 535

(b) Y. Q. Zheng, S. Q. Zhou and J. L. Lin, Z. Kristallogr. NCS; 216 (2001) 265

Introduction

45

(c) 118. 119. 120.

Y. Q. Zheng, A. Y. Pan and J. L. Lin, Z. Kristallogr. NCS; 216 (2001) 267

Y. J. Kim and D. Y. Jung, Inorg. Chem; 39 (2000) 1470 E. A. H. Griffith, N. G. Charles and E. L. Amma, Acta Crystallogr; B38 (1982) 262 (a) Y. Q. Zheng and J. L. Lin, Z. Kristallogr. NCS; 216 (2001) 139 (b) Y. Q. Zheng, J. L. Lin and W. J. Chen, Z. Kristallogr. NCS; 216 (2001) 269

121. 122. 123. 124. 125. 126. 127. 128. 129. 130. 131.

C. Livage, C. Egger and G. Ferey, Chem. Mater; 13 (2001) 410 Y. Kim and D. Jung, Bull. Korean Chem. Soc; 20 (1999) 827 Y. Kim and D. Jung, Bull. Korean Chem. Soc; 21 (2000) 656 E. V. Brusau, J. C. Pedregosa and G. E. Narda, J. Solid State Chem; 153 (2000) 1 E. V. Brusau, J. C Pedregosa and G. E Narda, J. Coord. Chem; 54 (2001) 469 C. Livage, C. Egger and G. Ferey, Chem. Mater; 11 (1999) 1546 R. Vaidhyanathan, S. Natarajan and C. N. R. Rao, Cryst. Growth Des; 3 (2003) 47 P. M. Forster and A. K. Cheetham, Angew.Chem. Int. Ed. Engl; 41 (2002) 457 J. Cano, G. Demunno, J. L. Sanz, and R. Ruiz, J. Chem. Soc. Dalton Trans; (1997) 1915 P. Chaudhuri, K. Order, K. Wieghardt, S. Gehring and J. Weiss, J. Am. Chem. Soc; 110 (1988) 3657 C. E. Xanthopoulas and M. P. Sigalus, Inorg. Chem; 32 (1993) 5433

46

Chapter 1

132. 133. 134. 135. 136. 137. 138. 139. 140. 141. 142. 143. 144. 145. 146. 147.

E. G. B. Bassis, J. Mrozinski, A. P. Bozpoulos and C. A. Tsipis, Inorg. Chem; 27 (1988) 529 E. G. B. Bassis, O. Kahn, S. Jeannin and Y. Jeannin, Inorg. Chem; 31 (1992) 625 C. S. Hong and Y. Do, Inorg. Chem; 36 (1997) 5684 O. Kahn and H. O. Stumf, Science; 261 (1993) 447 H. Okawa and C. Floriani, Angew. Chem. Int. Ed. Engl; 34 (1995) 1446 J. Lim and J. Kim, Angew. Chem. Int. Ed. Engl; 35 (1996) 998 M. Fujita and K. Ogura, Tetrahedron Lett; 40 (1991) 5589 H. Li and C. E. Davis, J. Am. Chem. Soc; 120 (1998) 2186 L. Deakin, A. M. Arif and J. S. Miller, Inorg. Chem; 38 (1999) 5072 D. Z. Liao, Z. H. Jiang and S. P. Yan, Polyhedron; 20 (2001) 681 Y. Liu, D. J. Xu and J. G. Liu, J. Cord. Chem; 54 (2001) 175 J. Cano, G. Demunno and M. Julve, J. Chem. Soc. Dalton Trans; (1994) 3465 J. Cano, G. Demunno and M. Julve, J. Chem. Soc. Dalton Trans; (1997) 1915 Y. T. Li, C. W. Yan and D. Z. Liao, Chinese J. Chem; 17 (1999) 467 J. C. Kim, J. H. Cho and A. J. Lough, Inorg. Chim. Acta; 317 (2001) 252 H. L. Zhu, Y. X. Tong, X. M. Chen and C. X. Ren, Trans. Metal. Chem; 26 (2001) 528

Introduction

47

148. 149. 150. 151. 152. 153. 154. 155. 156. 157. 158. 159. 160. 161.

L. C. Li, D. Z. Liao, Z. H. Jiang and S. P. Yan, J. Mole. Struc; 597 (2001) 157 L. C. Li, D. Z. Liao, Z. H. Jiang and S. P. Yan, Polyhedron; 20 (2001) 681 H. P. Xiao, M. L. Hu and X. H. Li, Acta Cryst; E60 (2004) m336 M. Kurmoo, H. J. Kumagai and M. A. Green, J. Solid State Chem; 159 (2001) 343 Z. L. Huang, M. Drillon, A. Sironi and P. Rabu, Chem. Mater; 12 (2000) 2805 O. R. Evans, G. K. Wong and W. Lin, Angew. Chem. Int. Ed. Engl; 38 (1999) 536 J. Tao, M. L. Tong and X. M. Chen, J. Chem. Soc. Dalton Trans; (2000) 3669 S. M. F. Lo, S. S. Y. Chui, X. X. Zhang and G. Wen, J. Am. Chem. Soc; 122 (2000) 6293 C. X. Zhang, F. Chen, C. B. Ma, M. Q. Hu, C. N. Chen and Q. T. Liu, Acta Cryst; C60 (2004) m288 P. L. Parikh and P. K. Bhattacharya, Indian J. Chem; 12 (1974) 402 S. Ramamoorthy and M. Santappa, J. Inorg. Nucl. Chem; 33 (1971) 1775 H. Sigel, Angew. Chem. Int. Ed. Engl; 14 (1975) 394 J. T. Groves and J. R. Olson, Inorg. Chem; 24 (1985) 2717 Carnet, Denniston Topping, Principles and Applications of Inorganic, Organic and Biological Chemistry; p 373-375

48

Chapter 1

162. 163. 164.

John R Holum, Fundamentals of General, Organic and Biological Chemistry; 6th Ed, (1996) 457 John R Holum, Fundamentals of General, Organic and Biological Chemistry; 6th Ed, (1996) 548 C. C. Mann and M. L. Plummer, The Aspirin wars, money, medicine, and 100 years of Rampant competition New York, Alfred A. Knopf, (1991) John R Holum, Fundamentals of General Organic and Biological Chemistry; 6th Ed, (1996) p.554 Henry Blackburn, Olestra and the FDA, The New England Journal of medicine, April 11, (1990), August 984 Ellin Doyle, Olestra The Jurys Still Out, Journal of Chemical Education; April (1997) 370 National Heart, Lung and Blood institutes, Public Health Service, National Institute of Health, US Dept. of Human Services, NIH Publc. 88-2696 (1987) W. Ernest and M. G. Christien, Chem. Rev; 99 (1999) 2451 A. R. Khokar, Y. J. Deng and A. B. Salaam, J. Inorg. Biochem; 51 (1993) 677 Sir. Geoffery Wilkinson, Comprehensive Chemistry Vol 2, (1987) p. 962-964 L. O. Tiffen, Plant Physiol; 41 (1966) 515 L. O. Tiffen, Biological Implications of Metals in the Environment, Proceedings of the 15th Annual Hanford Life sciences Symposium, Richland, USA, (1975), p. 315 G. L. Lyon, P. J. Peterson and R. R. Brooks, Planta; 88 (1969) 282 E. B. Finley and F. L. Cerklewski, Am. J. Clin. Nutr; 37 (1983) 553 Coordination

165. 166. 167. 168.

169. 170. 171. 172. 173.

174. 175.

Introduction

49

176.

E. G. Vergara, J. Hegenauer, P. Saltman, M. Sabat and J. Ibers, Inorg. Chim. Acta; 66 (1982) 115

177. J. C. Chang, L. E. Gerdom, N. C. Baenziger and H. M. Goff, Inorg. Chem; 22 (1983) 1739 178. J. A. Cooper, B. F. Anderson, P. D. Buckley and L. F. Voronkova, L. V. Mosina and Y. V. Yablokov, Russ. J. Inorg. Chem; 35 (1990) 1298 179. R. A. Anderson, J. H. Brantner, and M.M. Polansky, J. Agric. Food Chem; 26 (1978) 1219

180. R. D. Cannon and R. P. White, Prog. Inorg. Chem; 36 (1988) 195 181. A. Bino, D. C. Johnston, D. P. Goshorn, T. R. Halpert and E. I. Stiefel, Science; 241 (1988) 1479 182. 183. 184. A. Bino, R. Chayat, E. Pedersen and A. Schneider, Inorg. Chem; 30 (1991) 856 W. Frosch, S. Back, G. Rheinwald, K. Koheler, L. Zsolnai, G. Huttner and H. Lang, Organo metallics; 19 (2000) 5769 (a) A. M. Sladkov and I. R. Golding, Russ. Chem. Rev; 48 (1979) 868 (b) C. E. Housecroft, Coor. Chem. Rev; 115 (1992) 141 (c) C. E. Housecroft, Coor. Chem. Rev; 131 (1994) 1 (d) H. Lang, K. Kohler and S. Blau, Coord. Chem. Rev; 143 (1995) 113 185. 186. 187. W. R. H. Hurtely, J. Chem. Soc; (1929) 1870 L. Henk, Aalten, G.V. Koten, E. Riethorst and H. S. Casper, Inorg. Chem; 28 (1989) 4140 (a) W. Mayer and R. Fikentscher, Chem. Ber; 91 (1958) 1536

50

Chapter 1

(b) K. A. Cirigottis, E. Ritchie and W. C. Taylor, Aust. J. Chem; 27 (1974) 2209 188. (a) H. Stanely, Principles of (1987) 504 Organic Chemistry; 5th Edn,

(b) G. M. Rubottom, In Oxidation in Organic Chemistry, W. H. Tranhowsky, Ed; Academic Press, New York, (1982) 189. 190. 191. 192. 193. M. Michaclides, S. Skoulika and A. Aubrey, Angew. Chem. Int. Ed. Engl; 32 (1993) 1495 G. R. Desiraju, Crystal Engineering and the Design of Organic Solids; Elsevier, Amsterdam, (1989) D. Venkataraman, S. Lee, J. Zhang and J. S. Moore, Nature; 371 (1994) 591 J. Y. Lu, M. A. Lawandy and J. Li, Inorg. Chem; 38 (1999) 2695 L. Pan, N. Ching, X. Huang and J. Li, Inorg. Chem; 39 (2000) 5333

Chapter 2 Reagents and Physico-Chemical Methods

n this chapter an outline of the materials, procedures and various physico-chemical methods employed are presented.

2.1

Reagents
The metal salts used for the synthesis of the complexes were

BDH grade samples. The dicarboxylic acids used for the preparation of the parent 4-coordinated and 6-coordinated systems like succinic acid (H2suc), malonic acid (H2mal), oxalic acid (H2ox) and terephthalic acid (H2tpa) were either BDH or Merck make and used as such. The Lewis-bases used for the present study like pyridine (py), ethylenediamine (en), 1,3-propylenediamine (pn), 2,2'-bipyridine (bipy) and 1,10- phenanthroline (phen) were either BDH, fluka or E.Merck samples. The solvents employed for the present study were of BDH make and purified by standard procedures.(1) All the reagents and indicators used were prepared by standard procedure.

2.2
2.2.1

Preparative Details
Metal Dicarboxylates Metal dicarboxylates were generally prepared by reacting the

respective metal carbonate with a hot aqueous solution of the relevant dicarboxylic acid taken slightly in excess than required for 1:1 stoichiometry without adjusting pH. The reaction mixture was boiled on a steam bath for about 1h. The complex was separated and washed repeatedly with hot water followed by methanol.

52

Chapter 2

2.3

Elemental Analysis
All the metal dicarboxylates and their adducts were

characterised by elemental analysis. Various metal ions were estimated by standard procedures.(2) Representative procedures employed are given below for each metal ion. 2.3.1 Estimation of Nickel Weighed quantity (0.1g) of the complex was digested with con.H2SO4 followed by con.HNO3 to oxidise and decompose the organic matters. The clear solution so obtained was evaporated to dryness and the residue was extracted with distilled water. It was then diluted to 50 ml and 25 mg of murexide indicator was added followed by 5 ml of 1M NH4Cl solution. Ammonia solution was then added to it till pH was raised to 7 as indicated by the yellow colour of the solution. It was then titrated against standard EDTA solution. Near the end point, 5 ml of con.NH3 was added till the pH was 10 and the titration continued until the colour changed to violet.(2) 2.3.2 Estimation of Cobalt About 0.1g of the complex was digested with con.H2SO4 followed by con. HNO3 as before. A few drops of perchloric acid was also added to the resulting solution. The clear solution obtained was evaporated to dryness and the residue was then extracted with 50 ml of distilled water. Hexamine buffer was added to the resulting solution till pH was 6. It was then titrated against standard EDTA solution using xylenol orange indicator till the colour changes from red to yellow.(2)

Reagents and Physico-Chemical Methods

53

2.3.3 Estimation of Copper Weighed quantity (0.1g) of the complex was digested using con.H2SO4 and HClO4. The resulting clear solution was evaporated to dryness and the residue was then extracted with distilled water into an iodine flask. The Cu+2 solution thus obtained was brought to a pH of 4-5.5 by adding ammonia solution followed by acetic acid. The estimation of copper was done by iodometric titration using standard sodium thiosulphate solution and starch as indicator.(2) 2.3.4 Estimation of Carbon, Hydrogen and Nitrogen The conformation of the composition of all the adducts and metal dicarboxylates was done by estimating carbon, hydrogen and nitrogen by employing Heraeus CHN rapid analyzer.

2.4

Spectral Methods

2.4.1 IR spectra IR spectra were recorded using Shimadzu IR-470

Spectrophotometer operating in the range 4000-400 cm-1. The samples were prepared either in the nujol mull form or as KBr pellet. 2.4.2 Electronic spectra A ShimadzuUV-160A Spectrophotometer operating in the spectral range 1100-200 nm was used for electronic spectral studies. It has a accuracy of 2 nm. The spectra were recorded for the insoluble solid samples by making them as pasty mass by grinding with nujol and then spreading the paste uniformly on a

54

Chapter 2

transparent glass or a Whatman filter paper strip. The reference used was either a clean transparent glass or a Whatman filter paper strip wetted with nujol. For the soluble samples the spectra were recorded by dissolving them in CH3OH, water or CHCl3. The cuvettes used were of quartz make with path-length of either 1 cm or 0.5 cm. 2.4.3 EPR Spectra The X-band EPR spectra of the Cu(II) complexes recorded employing a Varian E-112 EPR were

spectrophotometer

operating at 9.1 GHZ with a microwave power of 5 mW. The field set is around 3000 G and the scan range used were either 2000 or 500 G. The spectra were obtained either at room temperature (for insoluble solid samples) or at liquid nitrogen temperature of 770K (for soluble samples). More often a methanol-toluene mixture was used as solvent to facilitate better glass formation at low temperature. DPPH or tetracyanoethylene (TCNE) radicals were used as g marker. The fundamental principles of EPR are essentially the same as those of NMR. Practical difference arises from the fact that the magnetic moment of an electron is substantially larger than that of proton. The energy of resonance absorption is E = h = gH . (2.1)

where denotes the frequency of the radiation used, h is Plancks constant, g is the spectroscopic splitting factor, is the Bohr magneton and H is the magnetic field.

Reagents and Physico-Chemical Methods

55

The various spin-Hamiltonian for the interaction of an electron with the magnetic field can be given by the equation = gHz . (2.2)

where g for a free electron has the value 2.0023, is Bohr magneton, eh/2mec with a value of 9.27310-21 erg gauss-1, z is the spin operator and H is the applied field strength. The spectra of powder samples result from the superimposition of all the orientations of single paramagnetic centers and has a shape influenced by the anisotropic part of the Hamiltonian. The nuclear spin of copper (I = 3/2) splits both the parallel and perpendicular lines into four hyperfine lines. The energy absorbed during a resonance transition h can be expressed as

h = gH + Am1

. (2.3)

For copper, the nuclear spin quantum number m1 takes values 3/2 and 1/2 We have analysed the EPR spectra of Cu complexes mostly by assuming axial symmetry for which the relevant spin Hamiltonian is

= gIIHzSz + g(HySy + HxSx) + AIIM SzIzM+ AM (SyIyM + SxIyM) + AIIN H

SzIzN + AN (SyIyN + SxIxN) . (2.4).

where z-axis is the symmetry axis of the molecule and S and I terms are components of the electron and nuclear spins in the specified directions. In equation (2.4), the first two terms are Zeeman for electron, third and fourth terms are the components due to the

56

Chapter 2

nuclear (metal) hyperfine interaction and fifth and sixth terms are contribution from the superhyperfine interaction of the ligand (N) and the unpaired electron. In a rigid medium each molecule has an orientation with respect to the magnetic field and the tensor g and the hyperfine coupling constant A can be written as
2 g = g ||2 cos 2 + g sin 2

. (2.5)

A=

(A g
2 ||

2 ||

cos2 + A g sin 2
2 2

.(2.6)

H || =

hv hv and H = g || g

. (2.7)

The hyperfine splitting arises because of the electron spin interacting with its own nucleus, and further to that the superhyperfine splitting due to the electron spin interacting with the nuclear spin of the neighbouring atom (s). The parallel and perpendicular components arise because of the anisotropy of the field felt at the free electron because of the overall structure of the molecule and also the orientation of the molecule with respect the external magnetic field applied. A can also be calculated from the equation
(3)

A=

g ||2 + A||2
2 2 g ||2 A||2 + g A

.(2.8)

Reagents and Physico-Chemical Methods

57

The average of g, ie., gav can be calculated from the equation gav = ( 2 3 ) g + ( 1 3 ) g || .(2.9)

It can be seen that for tetragonally compressed copper(II) complexes g > g where g = 2 and for tetragonally elongated copper(II) complexes g > g > 2. In a square planar copper(II) complexes if the unpaired electron resides in the dx2-y2 orbital, g>g>2 while g >g= 2 when the unpaired electron is in the dz2 orbital. The g is a parameter indicative of covalency. For a covalent complex g < 2.3 and for an ionic environment g = 2.3 or more. For a square planar copper(II) complex, the g value is expressed as
.

g = 2.002

2k and g = 2.002 E xz
2

2 8 k

E xy

(2.10)

where k is the orbital reduction factor, is the spin orbit coupling constant, Exz is the energy of 2B1g 2Eg transition and Exy is the
B

energy of 2B1g 2B2g. Combining the above two expressions

B B

G=

g 2.002 g 2.002

2 E xz 4 k 2 k E xy

(2.11)

The value of G indicates the strength of the ligand, whether strong or weak. If G < 4.0 the ligand forming copper (II) complex is regarded as a strong field ligand. In the case of Cu(II) complexes the
2 is related to A , g inplane covalency parameter Cu and g

according to Kivelson and Neiman equation.(4)

58

Chapter 2

2 = (A /0.036) + (g 2.002) + 3/7 (g - 2.002) + 0.04 ..(2.12) Cu 2 is in between 0.5 to 0.80 and for For covalent bonding, Cu 2 ionic it approaches 1. Cu is inversely related to the covalency of

the Cu-N bond. That means for a compound which has low value
2 , the covalency of the Cu-N bond is high or the ionic for Cu

character will be less. In the case of bonding, the ionic character increases as the nitrogen donor increases.

2.5

Coordination Chemistry of Copper(II)

Copper(II) forms complexes with coordination numbers four,

five and six, the latter being predominant. A significant number of 7 and 8 coordinate geometries also occur. Unlike other first row transition metal ions, the copper(II) complexes are characterised by a variety of distortions.(5,6) Majority of 6-coordinate copper(II) complexes involve an elongated tetragonal or rhombic octahedral structure, with a few involving a compressed tetragonal structure caused by Jahn-Teller effect. The tetrahedral geometry of Cu(II) ion always involves a significant compression along the S4 symmetry axis. Only the square planar geometry is regular for Cu(II) ion, but even there it involves a slight tetrahedral distortion. Copper(II) ions with five coordination rarely possess a regular square pyramidal geometry; it generally undergoes both an elongation and a trigonal in-plane distortion,(6) or less frequently, a tetrahedral distortion (J.T effect). The trigonal bipyramidal geometry of Cu(II) may be regular, but is frequently distorted slightly towards a square pyramidal stereochemistry.

Reagents and Physico-Chemical Methods

59

Generally, Cu(II) complexes are blue or green due to d-d electronic transitions causing absorption in the 600-900 nm regions. If there is a strong charge transfer band spreading to the visible region the complex appears red or brown. Since copper (II) ion is subjected to Jahn-Teller distortion and a regular octahedral complex is not formed, the formal Eg and T2g terms get splitted. The spectra do not usually correspond to the simple shown in Fig. 2.1.
2E g 2T 2g

excitation(7) but rather to one based on altered multiple states as

2 2

T2 g
2

Eg B2g 2 A1 g B1 g

D
2

Eg

Free ion

Octahedral
2

Tetragonally distorted

Fig. 2.1 Splitting of 2Eg and

T2g states in Cu(II) in various fields

Tetragonal copper(II) complexes are expected to show the transition band.(8,9) Four-coordinate Cu(II) complexes are common, but the
2B 1g
B

2A1g, 2B1g 2B2g and 2B1g 2Eg but bands due to

B B B

these transitions usually overlap to give often one broad absorption

strict tetrahedral or square planar stereochemistries are rare. Intermediate stereochemistry of approximate D2d symmetry is more usual and four transitions between the d-orbitals may be observed.(10,11) The spectra of such complexes often show two or

60

Chapter 2

three

less

resolved

bands

below

about

20,000

cm-1.

The

polarisation properties of these bands have been studied in some detail in certain cases assisting in the assignments of the transitions involved.(7,12)

2.6

Coordination Chemistry of Cobalt(II)

The most common states of cobalt are +2 and +3. A few Co(IV)

and Co(V) compounds also exist(13) such as golden yellow Cs2CoF6, red brown Ba2CoO4 and blue black K3CoO4. Most simple salts exist in the Co(II) oxidation state and crystallise from aqueous solution as CoX2.6H2O or CoX2.4H2O. Most Co(II) salts in aqueous solution readily dissociate to give the [Co(H2O)6]2+ ion which is pale pink. The existence of trication [Co(H2O)6]3+ is possible in very strong acids, which is blue in colour and is rapidly reduced by water to [Co(H2O)6],2+ liberating oxygen. Co(II) complexes adopt two major stereochemistries, six coordinate distorted octahedral and tetrahedral. Although a few low spin square planar systems are known cobalt phthalocyanines, cobalt(salen)-type Schiff bases as well as some five-coordinated systems such as [Co(CN)5]3- are square pyramidal with one unpaired electron; and [CoBr(N(C2H4NMe2)3)]+ is trigonal bipyramidal with three unpaired electrons. Octahedral and tetrahedral stereochemistries are often found in equilibrium and in aqueous solution even [Co(H2O)6]2+ has a small amount of [Co(H2O)4]2+ present. The d7 electronic configuration is the most favoured to form the tetrahedral as opposed to the octahedral stereochemistry. Ligand polarizability as well as ligand size are important factors, with the more polarizable ligands (eg. I, P, As, aromatic N donors) favouring

Reagents and Physico-Chemical Methods

61

tetrahedral structures. Most O and N (amine) donors, however, favour octahedral coordination. Octahedral Co(II) complexes are pink to violet in colour (absorption ~500 nm), whereas tetrahedral complexes are more intensely blue (~600 nm). The colour of octahedral Co(II) is dominated by 4T1g(F) 4T1g(P) transition (3), with the two lower energy transitions (to 4T2g (F) and 4A2g(F) levels), occurring in the near IR and visible regions of the spectrum respectively.(14) A simplified Orgel diagram for octahedral and tetrahedral cobalt(II) is shown in Fig 2.2 In octahedral systems the 4A2g level is usually close to the 4T1g(P) level and the transition to these two levels are close together. Since
4 4 the 4A2g state is derived from t 3 2 g e g and T1g(F) ground state is derived 2 4 4 from t 5 2 g e g configuration, T1g(F) A2g(F) transition is essentially a

two electron process. Hence it is weaker by about a factor of 10-2 than the other transitions. There is one more spin allowed transition in octahedral complexes which is the transition 4T1g(F) 4T2g(F).

T1(P)
4

P
4

T1g(P)

T1(F)

A2g (F)
4

T2 (F)
4

T2g (F)

F
4

T1g(F)

A2 (F) t 0

Fig 2.2 Orgel diagram for tetrahedral and octahedral Co(II)

62

Chapter 2

The T ground term results in temperature-dependent orbital contributions to the magnetic moment, with values (4.8-5.2 BM) falling off appreciably with decreasing temperature. Tetrahedral Co(II) is dominated by the broad and intense 3 transition
4A (F) 2

4T1(P) with the lower energy 1 and 2 transitions occurring (to 4T2(F) at 3000-5000 cm-1, to 4T1(F) at

in the near IR region

5000-8000 cm-1). The spin only moment of 3.87 BM for the tetrahedral ligand field is modified by mixing the lower energy 4T2(F) level into the ground 4A2 term via spin-orbit coupling, and this results is greater than spin only magnetic moments (15-25%) depending on the ligand; the moment is temperature independent in this case.

2.7

Coordination Chemistry of Nickel(II)

Nickel compounds have been found to occur with the metal

in oxidation states varying from -1 to 4.(15) However, comparatively very few compounds correspond to the lowest (-1) and to the higher (+3, +4) oxidation states. Ni(-1) has been claimed to be formed only in a few organometallic compounds.(16) The reported Ni(0) complexes are all diamagnetic which show the ligands stabilise the 1S (3d10) configuration relative to the other ones.(17) Ni (+1) complexes are also comparatively rare similar to Ni(-1) and are paramagnetic (d9 configuration, eff = 1.72-2.4 BM). The coordination overwhelming numbers of majority four, of Ni(II) or six. complexes Complexes have with

five

coordination numbers of 3,7 and 8 are still quite rare. In almost all its six-coordinated complexes of nickel(II) has a pseudo octahedral stereochemistry with a spin triplet as ground state (high spin

Reagents and Physico-Chemical Methods

63

configuration). The magnetic moments of octahedral Ni(II) usually lie between 2.9 and 3.3 BM and the temperature dependence of the magnetic susceptibilities follow Curie-Weiss law. Five-coordination is also now quite common in Ni(II) complexes and many polydentate ligands such as polyamines, salicylaldimine polyarsines and polyphosphines have been designed with the purpose of favouring this stereochemistry.(18,19) However, five-coordinate complexes with monodentate

ligands [Ni(CN)5]3- and [Ni(OAsMe)5]2+ are also known. The five coordinate Ni(II) complexes have structure which are generally near to one of the two limiting geometries, namely the square pyramid and trigonal bipyramid. The electronic ground state of Ni(II) in five coordinated complexes can neither be a spin singlet or a spin triplet. Spin singlet corresponds to low spin configuration while spin triplet to high spin configuration. The majority of 4-coordinated nickel(II) complexes are square planar and invariably diamagnetic, whereas pseudo tetrahedral complexes which are always paramagnetic are relatively rare. It is in general found that ligands with weaker donor strengths favour a pseudo tetrahedral structure, whereas ligands with higher donor strengths tend to produce square planar structure. It must also be borne in mind that ligands which contains bulky substituents on the donor atoms may prevent a planar structure due to steric hindrance, and a distorted tetrahedral structure may become preferred.(20) Nickel(II) in tetrahedral geometry has an orbitally degenerate ground state and the magnetic moments are expected to be substantially higher than those of six-coordinate complexes

64

Chapter 2

because of large orbital contribution. The magnetic moments are usually found to be in the range 3.3-4 BM at room temperature. Strong Ni-ligand interactions stabilise planar configuration in 4-coordinated Ni(II) complexes. Planar complexes of Ni(II) are often yellow owing to an absorption around 500 nm. The majority of square planar complexes are formed by interacting either chelating ligands or tetradentate macrocyclic ligands with Ni(II). Porphyrins and phthalocyanines also stabilise square planar and octahedral Ni2+ complexes.

Fig.2.3

d-orbital splitting patterns and electron occupation for Ni2+ in tetrahedral, octahedral, tetragonally distorted and square planar geometries.

Another common feature of square planar Ni(II) complexes is their ability to coordinate extra ligands in solution to set up equilibria between four, five and six-coordinated complexes. Thus diamagnetic square planar complexes can be transformed in coordinating solvents or in the presence of extra ligands to

Reagents and Physico-Chemical Methods

65

paramagnetic octahedral Ni(II) species. The electronic spectral features of nickel have been thoroughly reviewed.(19-21) Tetrahedral complexes are usually highly coloured due to their expected d-d transition from 3T1(F) state to 3T2(F) (1), to 3A2 (F) (2) and to 3T1(P) (3), respectively. But the observed spectra tend to be complicated by spin-orbit coupling effects. Three d-d transitions resulting in
3A (F) 2g 3A (F) 2g

3T (F) 2g

(1),

3T1g(F) (2) and 3A2g(F) 3T1g(P) (3), would be observed for

Ni(II) in an octahedral field. The simplified Orgel diagram for tetrahedral and octahedral Ni(II) is shown in Fig 2.4. Ni(II) square planar complexes have a single band in the range 18000-25000 cm-1 due to transition for 1B1g 1A1g.(21)
B

Fig. 2.4

The simplified Orgel diagram for Ni (II) in tetrahedral and octahedral ligand fields

66

Chapter 2

2.8

Thermal Analysis
Thermal methods of analysis have become an important tool

in the study of solid state reactions, phase equilibria, measurement of specific heat etc. The study of the reactions involving solids has three aspects, viz., phenomenological, thermodynamic and kinetic. The phenomenological study is mostly concerned with the quantitative and semiquantitative observations occurring during the reactions. The thermodynamic aspect is static in nature. It is related to the initial, final and equilibrium states of the system and the driving force behind the transformations. The kinetic approach is mainly concerned with the rate of transformations of the reactants into the products and the mechanism of transformations. The present investigation involves mainly the study of the influence of procedural factors on kinetic parameters obtained from nonisothermal kinetic analyses using TG and DTG data. 2.8.1 Thermogravimetry (TG) The present thermal experiments were carried out using Seiko thermal analyser in an atmosphere of dry nitrogen, from room temperature to about 8000C. The kinetic parameters were calculated by using a computer programme. Thermogravimetry is defined as a technique whereby the change in mass of a substance is recorded as a function of time or temperature, as it is heated or cooled in a suitable environment at a controlled rate. Mainly two methods are employed in thermogravimetry: (1) isothermal or static thermogravimetry, where the sample mass is recorded as a function of time at constant temperature and (2) non-isothermal or dynamic thermogravimetry,

Reagents and Physico-Chemical Methods

67

where the sample is heated in an environment whose temperature is changing in a linear rate. In derivative thermogravimetry (DTG) the derivative of mass change with respect to time is recorded as a function of time or temperature. The derivative curve may be obtained either from the TG curve by manual differentiation methods or by electronic differentiation of the TG signals. The area under the DTG peak at any temperature gives the rate of mass change at that temperature. The DTG curve allows the ready determination of the temperature at which the rate of mass change is maximum (Ts) and the initial temperature (Ti) at which cumulative mass change begins and the final temperature (Tf) at which the cumulative mass change reaches a maximum corresponding to complete reaction. 2.8.2 Differential Thermal Analysis (DTA) DTA is a thermal technique in which the temperature of a sample is compared with the temperature of a thermally inert material and the temperature difference is recorded as a function of the sample or furnace temperature, as the sample is heated or cooled at a uniform rate. The temperature changes in the sample are due to endothermic or exothermic reactions that occur during the temperature programme and the corresponding deviation from the reference temperature is studied. This difference in temperature between the sample and the reference, i.e., T= Tsample-Tref is recorded as a function of temperature.

68

Chapter 2

In non-isothermal method, the following aspects are studied. a) Phenomenological Aspects: This study is used to find the initial temperature (Ti), the final temperature (Tf) and the temperature of maximum mass loss (Ts) from DTG peaks. The TG plateau gives the percentage mass loss during each stage of decomposition. The DTA curve identifies the exothermic or endothermic nature of the different changes undergone by the sample. b) Kinetic Aspects: One of the most important applications of thermogravimetry involves the study of reaction kinetics and mechanism of solid state thermal decomposition reactions. The reaction rate of a solid thermal decomposition can be expressed by the general equation(22)

d E = A. exp . f ( ) dt RT

. (2.13)

where, A = pre-exponential factor, t = time, and = fractional decomposition. E= activation energy. The f () = depend on the mechanism of the reaction.

W0 W W0 Wt

(2.14)

where, W0, W and Wt are initial, actual and final sample weights respectively.

Reagents and Physico-Chemical Methods

69

When the temperature of the sample is increased at a constant rate of =

dT , we can write dt
(2.15)

d A -E = exp f ( ) dT RT
or as

d A -E = exp dT f ( ) RT
On integration

. (2.16)

g () =
0

d A = f ( )

T 0

dT exp RT

.(2.17)

where g () is the integrated form of f () or, ln g () =

E AR + ln RT E

.(2.18)

Plotting the LHS of equation 2.18 against 1/T should give a straight line with a slope of -E/R irrespective of g() values employed. The kinetic parameters can be calculated from the same linear plot. The value of E and A can also be evaluated from the slope and intercept respectively. The entropy of activation (S) could be calculated from the equation.

A= where

k .Ts S exp R h

.(2.19)

k = Boltzmann constant, h = Plancks constant S = entropy of activation.

70

Chapter 2

c) Mechanism of reaction from non- isothermal TG: Deduction of the mechanism or reaction from non-isothermal methods has been discussed by Sestak and Berggren.(23) Kinetic parameters are evaluated from non-isothermal TG curves by the application of Arrhenius equation. The usual non-mechanistic kinetic equations are extension of those used in homogenous kinetics, where it is assumed that f () = (1-)1-n and mechanistic and kinetic studies are based on the assumption that the form of g() depends on the reaction mechanism. A series of f() forms are proposed and the mechanism is obtained from the one that gives the best representation of the experimental data. Four non-mechanistic methods are usually used for the calculation of kinetic parameters from the TG curve. The forms of these equations used are given below, where the term g() has been introduced for convenience and defined as.

g() =

1 (1 )1 n 1 n
(22)

. (2.20)

1. Coats-Redfern equation

In

AR 2 RT E g ( ) (1 ) = ln 2 E T E RT
(24)

. (2.21)

2. Mac Callum-Tanner equation

log10 g() = log10

AE 10 3 0.435 [0.499 + 0.217 E ] 0.485 E ...(2.22) T R

Reagents and Physico-Chemical Methods

71

3. Horowitz Metzger equation

(25)

s In g () = In E - RT + ET s s

ART

Ea

... (2.23)

4. MKN equation

(26)

ln

AE g ( ) = ln 1.9215 + 3.7721 - 1.9215 ln E - 0.12039 R T

E T

...(2.24)

where = fraction of decomposition, n = order parameter, T = temperature in Kelvin, A = pre-exponential parameter, = heating rate in 0C min-1, E = activation energy, R = gas constant, Ts = DTG peak of the reaction. The kinetic parameters can be calculated from the linear plot of the LHS of the kinetic equation against 1/T for equation 2.21, 2.22 and 2.24 and against for equation 2.23. The value of E and A are calculated from the slope and intercept respectively. The Coats-Redfern equation (eqn.2.21) was used for solving the exponential integral in the present study because it is one of the best approaches recommended by several authors.(27-29) Satava(30) listed nine probable reaction mechanisms from the Coats-Redfern equation which are given in Table. 2.1. temperature, = (T-Ts), M = mass loss in TG experiment, a = area of DSC curve at time t and after the completion

72

Chapter 2

Table 2.1 Mechanism based equations

Eqn. No 1 2 3 2 + (1-) In (1-) [1-(1-)1/3]2
2 3

Form of g ()

Rate Controlling process One- dimensional diffusion Two- dimensional diffusion Three-dimensional diffusion, spherical symmetry, Jander equation. Three dimensional diffusion, spherical symmetry, Ginstling- Brounshetin equation Random nucleation, one nucleus on each particle, Mampel equation Random nucleation, Avrami equation I Random nucleation, Avrami equation II Phase boundary reaction, cylindrical symmetry Phase boundary reaction, spherical symmetry

(1

) (1 )2 / 3

5 6 7 8 9

-In (1-) [-In (1-)]1/2 [-In (1-)]1/3 1- (1-)1/2 1-(1-)1/3

2.9

Magnetic Susceptibility Measurements

Magnetic moment of all the complexes were measured at

room temperature (282)0C using Gouy balance with mercury(II) tetrathiocyanatocobaltate(II) as calibrant. Magnetochemistry is used to investigate the magnetic properties of transition metal complexes. Magnetic moment can provide information about the oxidation state of the metal ion, electronic structure and symmetry properties of the complexes. This also would give a clear idea about

Reagents and Physico-Chemical Methods

73

the number of unpaired electrons in the central metal atoms or ion in the complex. In first row transition metals, the spin only magnetic moment can be calculated using the equation (s,o) = [ 4S (S+1)]1/2 ..(2.25)

The magnetic susceptibilities of the complexes were measured at room temperature using a Gouy magnetic balance. The Gouy tube was standardised(31) using mercury(II) tetrathiocyanatocobaltate(II). Diamagnetic corrections for the rest of the molecules were computed from Pascals constants.(32,33) Gram susceptibility was calculated using the formula. g =

+ E
W

.. (2.26)

where = air displacement constant, = Gouy tube constant E = change in weight in mg, W = weight of the sample in gram The effective magnetic moments, eff, were calculated from corrected molar magnetic susceptibility, m*. m = g mol. wt m* = m + D where, D is the diamagnetic correction
* T BM eff = 2.84 m

(2.27)

. (2.28)

74

Chapter 2

References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. Vogels Text Book of Practical Organic Chemistry, ELBS, IVth Edn, London (1978) A. I. Vogel, A Textbook of Quantitative Inorganic Analysis; ELBS, London (1978) H. R. Gersman and J. D. Swallen, J. Chem. Phys; 36 (1962) 12 D. Kivelson and R. Neiman, J. Chem. Phys; 135 (1961) 149 B. J. Hathway and D. E. Billing, Coord. Chem. Rev; 5 (1970) 143 B. J. Hathway, Structural Bonding, (Berlin), Volume 57 (1984) p. 55 M. A. Hitchman, Trans. Met. Chem; 9 (1984) 1 Y. Nishida and S.Kida, Coord. Chem. Rev; 15 (1975) 279 R. Sreekala and K. K. M. Yusuff, Synth. React. Inorg. Met-Org. Chem; 24 (1994) 1773 J. Ferguson, Prog. Inorg. Chem; 12 (1970) 159 A. B. P. Lever, Inorganic Electronic Spectroscopy, 2nd Edn. Elsevier, Amsterdam, (1984) N. S. Hugh and R. J. M. Hobbs. Prog. Inorg. Chem; 10 (1968) 259 W. Levason and C. A. M. Auliffe, Coord. Chem. Rev; 12 (1974) 151 R. L.Carlin, Trans. Met. Chem; 1 (1965) 1 F. A. Cotton and G. Wilkinson; Advanced Inorganic Chemistry; 4th Ed. Wiley Interscience, New York 785, (1980) K. Nag and A. Chakravorthy, Coord. Chem. Rev; 33 (1980) 87 L. Malatesta and S. Cenini, Zero-Valent Compounds of Metals, Academic Press, London (1974)

Reagents and Physico-Chemical Methods

75

18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33.

R. L. Orioli, Coord. Chem. Rev; 6 (1971) 285 R. Morassi, Bertini and L. Sacconi, Coord. Chem. Rev; 11 (1973) 343 E. Uhling. Coord. Chem. Rev; 10 (1973) 227 A. B. P. Lever, Inorganic Electronic Spectroscopy, Elsevier, Amsterdam (1968) A. W. Coats and J. P. Redfern, Nature; 201 (1964) 68 J. Sestak and G. Berggren, Thermochim. Acta; 3 (1971) 1 J. R. M. Callum and J. Tanner, Eur. Polym. J; 6 (1970) 1033 H. H. Horowitz and G. Metzger, Anal. Chem; 35 (1963) 1964 P. M. Madhusudanan, K. Krishnan and K.N. Ninan, Thermochim. Acta; 97 (1986) 189 M. D. Juddo and M. T. Pope, J. Therm. Anal; 4 (1972) 31 J. Zsako, J. Therm. Anal; 5 (1973) 239 Y. M. Gorbachev, J. Therm. Anal; 8 (1975) 349 V. Satava, Thermochim. Acta; 2 (1971) 423 B. N. Figgis and R. S. Nyholm, J. Chem. Soc; (1958) 4190 B. N. Figgis and J. Lewis, Progress in Inorganic Chemistry, (Ed, F.A Cotton), Interscience, New York, 6, 37, (1964) A. Earnshaw, Introduction to Magnetochemistry, Academic Press, London, (1968)

Chapter 3 Interaction of Lewis-bases with Polymeric Metal(II) Succinates

3.1

anti-anti, monoatomic) and bridging with metal-metal bond(s), besides its ability to function as non-coordinating anions. Experiments show that the interchange of these linking modes can happen with comparative ease depending on various conditions. Consequently metal complex systems with innumerable structural diversities could be accomplished by appropriate synthetic manipulations. Mention also has been made in the previous chapter about the ability of dicarboxylate systems to generate multitudes of extended structural forms with interesting topologies, because of their bi-functional nature and also due to their ability to coordinate in many of their combinatorial forms.(1-3) As indicated, one of the main thrusts in the present study is the generation of polymeric metal dicarboxylates and their interaction with neutral Lewis-bases. It has been amply demonstrated that dicarboxylate systems containing varying spacer moieties interact with metal ions yielding variety of novel supramolecular architectures, whose structural features and dimensionality get dictated by the metal ion, spacer function between the carboxylate groups, the additional coligands and reaction conditions.(4-6) Succinic acid (H2suc), HOOC-CH2-CH2-COOH, is one of the readily available dicarboxylic acids and it contains -CH2-CH2- as spacer between the two carboxylic acid functions. Because of the sp3 hybridised nature of both the C atoms in -CH2-CH2- moiety, the

Introduction
n Chapter 1 we have discussed in detail the diverse ligation modes possible for the carboxylate moiety which include the monodentate, bidentate chelating, bridging (syn-syn, syn-anti,

78

Chapter 3

connected COOH groups can get easily disposed in various directions with respect to each other. Besides its ability to keep the coordinated metal atoms at a convenient distance above 5.5 if each carboxylate function is coordinated to a single metal ion, the flexible nature of the -CH2-CH2- spacer moiety can have the metal centres oriented in varieties of forms. In addition the versatility of the ligation modes of the carboxylate function and their easy accessibility and interchangeability, the presence of any additional ligands can also make metal succinate a very interesting network system. A brief mention has been made in the introductory chapter about some of the metal succinate systems exhibiting interesting structural diversities.(7-9) Besides its ability to yield polymeric 1D chain,(10-12) the succinate dianion can also polydentately link metal ions to form multivarious 2D and 3D networks.(13-16) The possibility of self-assembly of transition metal ions with succinate anions to generate interesting framework structures under hydrothermal synthetic conditions have been probed by several workers.(17-19) Several open framework transition-metal succinates structures as in [Fe5(OH)2(suc)4](20c), with edge and sharing MO6 (M=Co, Mn, Fe) octahedra are known.(20) Some of the [Co5(OH)2(suc)4](17) [Co4(OH)2(H2O)2(suc)3].2H2O(18) are particularly interesting. In 1966 Figgis and Martin(21) had reported a copper-succinate complex with composition [Cu(H2O)2(suc)]n and postulated a polymeric structure made up of chains of cupric acetate type dimers. However so far its structural proof was not forthcoming. Several interesting of various ferrimagnetic behaviour was seen in many of cobalt succinate systems.(17,18) Recently, cadmium succinates dimensionalities have been reported.(22) In these, a tetrahedral [Cd(suc)4]6- building unit yields 1D and 3D structures. The

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

79

interesting

3D

structures

as

in

[Cd3(OH)2(suc)2](22)

and

[Cd(OH)2(suc)](16) possess the interpenetrated diamondoid topology. Forster et al(23) has reported an interesting heptanuclear Ni system, [Ni7(OH)2(suc)6(H2O)2].2H2O which has been shown to have a honeycomb like structure and was prepared at the interface of a water/cyclohexanol mixture. This compound exhibits an infinite Ni-O-Ni framework and has 1D hydrophobic channels. Several mixed ligand complexes with 1D zig-zag chain like structures have been reported.(24-27) The 1D and 3D structures seen in [Mn(suc)(bipy)(H2O)2].12H2O(28) [Mn(suc)(phen)(H2O)3].2H2O(29) and [Co(suc)(phen)2(H2O)].1.5H2O(30) are also interesting as in these complexes one carboxyl group of the suc dianion is coordinated to the metal(II) atom as a monodentate while the other carboxyl group is seen to be non-coordinating. Recently Rao et al(31) reported a cube like architecture, Na3[Cd5(suc)6X] (X= Cl, Br) in which the tetrahedral [XCd4O24] clusters are found to be connected through succinate linker groups. In [Cu2(phen)2(OH)2]suc.8H2O(32) the suc dianion is seen to be in non-coordinated form whereas in [Cu2(suc)(phen)2(NO3)2(H2O)2](33), the suc dianion is found to be functioning as bidentate bridging with a layer structure. polymeric interesting employed metal succinates and their The are Lewis-base various In the present chapter we discuss the structural features of some of the mediated fragmentation or modification to yield compounds that can have framework in the structures. study Lewis-bases (en), present ethylenediamine

2,2'-bipyridyl (bipy), 1,10-phenanthroline (phen), 1,3-diaminopropane (pn) and pyridine (py) which are either chelating, conjugatively chelating or monodentate in nature.

80

Chapter 3

3.2

Experimental

3.2.1 Reagents used Succinic acid, CuCO3Cu(OH)2.H2O, NiCO32Ni(OH)2.4H2O, used were of Merck

CoCO3, pyridine, 2, 2'- bipyridine, 1,10-phenanthroline monohydrate, ethylenediamine and 1,3-diaminopropane purification by reported procedure.(34) 3.2.2 Preparation of metal(II) succinates Metal succinates of Ni(II), Co(II) and Cu(II) were prepared by the procedure reported by Allan et al.(35) The method involved The solid reacting the appropriate metal carbonate with a hot aqueous solution of succinic acid in stoichiometric quantities. complexes were filtered after digestion for 3 h. They were washed repeatedly with hot water and methanol and dried under vacuum over P2O5. (a) Nickel(II) succinate complex, [(Ni(suc)(H2O)2).2H2O]n, 1 To an aqueous solution of succinic acid (0.12g, 1mM), nickel carbonate (0.37g, 1mM) was added slowly with stirring. Brisk effervescence was formed indicating the reaction and formation of complex. The reaction mixture was boiled on a steam bath for about 30 min. The amount of nickel carbonate added was slightly less than the stoichiometric amount of succinic acid used. The green complex formed was filtered and washed repeatedly with hot water to remove any excess of succinic acid present and finally with methanol. The pure complex thus obtained was dried in vacuo. (yield : 90%) quality. Methanol, diethyl ether and acetone were used after

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

81

(b)

Cobalt(II) succinate complex, [(Co(suc)).2H2O]n, 2 Cobalt carbonate (0.12g, 1mM) was added in small

quantity with stirring to a hot aqueous solution of succinic acid (0.12g, 1mM). The amount of CoCO3 was kept slightly greater than stoichiometric amount of succinic acid. Unlike nickel succinate a clear pink coloured solution was obtained on the addition of the metal salt into the succinic acid solution. A slight excess CoCO3 was added to the clear solution obtained to check the completion of reaction. Any excess cobalt carbonate present was removed by repeated filtration. The complex was separated by concentrating the filtrate on a steam bath and it was purified by recrystallisation from hot water. The violet complex obtained was dried under vacuum. (yield : 85%) (c) Copper(II) succinate complex, [Cu(II)suc]n, 3 The procedure adopted for the preparation of copper(II) succinate complex was almost the same as that of nickel(II) succinate complex. About 0.23g (1mM) of cupric carbonate was added in small quantity to a hot aqueous solution of (0.12g, 1 mM) succinic acid while stirring. The amount of cupric carbonate used was slightly less than the stoichiometric amount of succinic acid. The reaction mixture was boiled on a water bath. The turquoise blue complex formed was filtered and was washed repeatedly with hot water to remove excess acid and finally with methanol. It was dried under vacuum over P2O5. (yield : 90%)

82

Chapter 3

3.2.3 (a)

Preparation of Lewis-base adducts of nickel(II) succinate [Ni(en)2(H2O)2]suc.2H2O, 4 A solution of en (0.13 ml, 2mM) in methanol was added

dropwise to a suspension of nickel(II) succinate (0.24g, 1mM) in methanol with constant stirring for about half an hour. After 30 min a clear violet solution was obtained which was filtered and then concentrated to half of its volume and cooled. The complex was separated as violet solid. This was filtered and was repeatedly washed with diethyl ether and dried in vacuo. (yield : 80%) (b) [Ni(bipy)2(H2O)2] suc.2H2O, 5 A solution of 2,2'-bipy (0.31g, 2mM) in methanol was added dropwise to a suspension of nickel(II) succinate (0.24g, 1mM) in methanol. The mixture was kept under reflux for about 30 min. A clear light violet solution was obtained which was filtered and concentrated to half of its volume and then cooled. The complex separated out as light violet solid which was then filtered. This was repeatedly washed with ether and dried under vacuum over P2O5. (yield : 80%) (c) [Ni(phen)2(H2O)2]suc. 2H2O, 6 The method adopted for the preparation of this adduct was almost similar to that employed for the 2,2'-bipyridine complex. The clear light violet solution obtained after reflux with 0.4g (2mM) of phen for about 30min was concentrated to half of its volume and cooled. The complex gets precipitated as light violet powder which was filtered. It was repeatedly washed with ether and dried in vacuo. (yield : 85%)

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

83

(d)

[Ni(py)(H2O)suc]n, 7 A solution of pyridine (0.48ml, 3mM) was added to a

nickel(II) succinate (0.48g, 1mM) suspension in methanol with constant stirring. The reaction mixture was refluxed for about 2 h. A clear green solution was obtained from which solid bluish green complex was found to be separated out, soon making the supernatent liquid colourless. The solid complex was filtered and was repeatedly washed with methanol followed by ether. This was dried in vacuo. (yield : 75%) (e) [Ni(pn)2(suc)]n, 8 A solution of pn (0.18ml, 2mM) in methanol was added dropwise to a suspension of nickel(II) succinate (0.24 g, 1mM) in methanol with constant stirring for about half an hour. A clear light violet solution was obtained from which solid light violet complex was found to be separated out soon making the supernatent liquid colourless. The solid complex was filtered and repeatedly washed with methanol followed by acetone. dried in vacuo. (yield : 80%) 3.2.4 Preparation of Lewis-base adducts of cobalt(II) succinate (a) [(Co(en)2suc).H2O]n, 9 A solution of en (0.13ml, 2 mM) in methanol was added to a suspension of cobalt(II) succinate (0.21g, 1mM) in methanol with constant stirring for about 1 h. A clear brown solution was obtained which was filtered and was concentrated to half of its volume. On cooling a pasty mass was obtained which on stirring with ether light brown complex was separated out. It was filtered and washed repeatedly with ether and dried in vacuo. (yield : 70%) This was

84

Chapter 3

(b)

[Co(bipy)2(H2O)2]suc.2H2O, 10 A solution of 2,2'-bipy (0.31g, 2mM) in methanol was added

dropwise to a suspension of cobalt(II) succinate (0.21g, 1mM) in methanol. The mixture was kept under reflux for about 30 min. A clear brownish orange solution was obtained which was filtered and concentrated to half of its volume and cooled. The complex separated out as orange brown solid was filtered and repeatedly washed with ether. It was dried under vacuum over P2O5. (yield : 80%) (c) [Co(phen)2]suc.2H2O, 11 A solution of phen (0.4g, 2mM) in methanol was added dropwise to a suspension of cobalt(II) succinate (0.21g, 1mM) in methanol. The mixture was kept under reflux for about half an hour. A clear orange solution was obtained which was filtered and was concentrated to half of its volume and cooled. The light orange complex was separated out by filtration. It was washed repeatedly with ether to obtain the pure complex. This was dried in vacuo. (yield : 85%) (d) [Co(py)2suc]n, 12 A solution of pyridine (0.48ml, 3mM) in methanol was added to a cobalt(II) succinate (0.42g, 1mM) suspension in methanol with constant stirring. The colour of the complex changed instantaneously from violet to pink. The reaction mixture was refluxed for about 3 h. The pink complex was separated out by filtration. It was washed repeatedly with hot methanol followed by diethyl ether. The complex was finally dried in vacuo. (yield : 80%)

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

85

(e)

[(Co(pn)2suc).H2O]n, 13 A solution of pn (0.18ml, 2mM) in methanol was added

dropwise to a suspension of cobalt(II) succinate (0.21g, 1mM) in methanol with constant stirring for about 1 h. A clear dark brown solution was obtained which was concentrated to half of its volume and cooled. A pasty mass was obtained which on stirring with acetone brown complex was separated. It was filtered and repeatedly washed with acetone. This was dried in vacuo. (yield : 70%) 3.2.5 Preparation of Lewis-base adducts of copper(II) succinate (a) [Cu(en)suc]n, 14 A solution of en (0.13ml, 1mM) in methanol was added dropwise to a suspension of copper(II) succinate (0.34g, 1mM) in methanol with constant stirring for about 2 h. The immediate colour change of the complex from turquoise blue to violet gives a clear indication of the adduct formation. The complex was separated by filtration and purified by repeated washing with methanol followed by diethyl ether. It was dried in vacuo. (yield : 80%) (b) [Cu(en)2(H2O)2]suc, 15 A solution of en (0.13ml, 2mM) in methanol was added dropwise to a suspension of copper(II) succinate (0.17g, 1mM) with constant stirring for about 1 h. A clear dark violet solution was obtained which was filtered and concentrated to half of its volume and then cooled. The violet complex formed was separated out by filtration and was purified by washing several times with ether. The compound was dried under vacuum over P2O5. (yield : 85%)

86

Chapter 3

(c)

[Cu(bipy)suc]n, 16 A solution of 2,2'-bipy in methanol (0.31g, 2mM) was added

dropwise to a suspension of copper(II) succinate (0.17g, 1mM) in methanol with stirring. The mixture was kept under reflux for about half an hour. A clear dark blue solution was obtained from which a large amount of light blue solid was found to be separated out leaving the supernatent liquid colourless. The complex was filtered and washed repeatedly with methanol followed by diethyl ether. This was dried in vacuum. (yield : 75%) (d) [Cu2(phen)4suc]suc.12.5H2O, 17 To a suspension of copper(II) succinate (0.17g, 1mM) in methanol, a solution of 0.4g (2mM) of phen dissolved in 15ml methanol was added with stirring. The reaction mixture was kept under reflux for about 30 min. A clear green solution was obtained. It was filtered and was concentrated to half of its volume and cooled. The light green complex formed was separated out by filtration and was washed repeatedly with ether to obtain the pure complex. This was dried in vacuo. (yield : 80%) (e) [Cu(py)2suc]n, 18 A solution of pyridine (0.48ml, 3mM) in methanol was added to a copper(II) succinate suspension (0.34g, 1mM) in methanol with stirring. The reaction mixture was refluxed for about 3 h. The colour change of parent complex from blue to green gave clear indication of the formation of new adduct. The green complex formed was separated out by filtration and was washed several times with hot methanol followed by ether. vacuum over P2O5. (yield : 75%) It was dried under

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

87

(f)

[Cu(pn)suc]n, 19 A solution of pn (0.17ml, 1mM) in methanol was added

dropwise to a suspension of copper(II) succinate (0.34g, 1mM) in methanol with constant stirring for about 2 h. The colour change of the parent complex from turquoise blue to dark blue gave indication of the formation of the adduct. After the reaction, the supernatant liquid in the reaction flask was found to be colourless. The dark blue complex formed was separated out by filtration and was washed several times with methanol followed by acetone. It was dried in vacuo. (yield : 85%) (g) [Cu(pn)2(H2O)2]suc, 20 A solution of pn (0.18ml, 2mM) in methanol was added dropwise to a suspension of copper(II) succinate (0.17g, 1mM) in methanol with constant stirring for about half an hour. A clear dark violet solution was obtained which was filtered and was concentrated to half of its volume and then cooled. The complex formed was separated out as violet solid and was filtered. This was washed repeatedly with acetone and dried in vacuo. (yield : 80%) 3.2.6 Analytical Methods All the complexes were analysed for the metal content by the volumetric method. Copper was estimated iodometrically; cobalt and nickel were estimated complexometrically.(36) The IR spectra of the complexes and their adducts were recorded in the range 400-4000 cm-1 on a Shimadzu IR 470 spectrophotometer. Electronic spectra were recorded in the solid state as nujol mull paste technique employing a Shimadzu UV 160 A spectrophotometer in the range 200-1100 nm. The C, H and N analysis were carried out using

88

Chapter 3

Heraeus CHN rapid analyser. The magnetic susceptibilities were measured on a Sartorious semimicro Guoy balance. Hg(Co(SCN)4) was used as the calibrant.

3.3

Results and Discussion

3.3.1 Metal succinates of Ni(II), Co(II) and Cu(II) The preparative procedure known earlier for generating metal(II) succinates involved mainly reacting respective metal carbonates with succinic acid, H2suc, without adjusting any pH.(35,37) However, it was seen that the water of crystallization varied from 0 to 4 depending on the nature of metal succinate.(21,38,39) Besides the reported metal carbonate route, we have tried the synthesis by using other metal salts precursors also. The latter methods are also seen to be rather facile when we adjust the reaction pH. The reactions involved could be summarized as below. MCO3 + H2(suc) M(suc) + CO2 + H2O MX2 + H2(suc)+2 NaOH M(suc) + 2H2O + 2NaX [M = Cu(II), Co(II), Ni(II) and X = Cl] Analysis of the various metal succinates obtained was carried out by known procedures and the data show a strict 1:1 composition (metal : suc) for all the succinate complexes of divalent metal ions (Table 3.1). The metal succinates obtained, [M(suc).nH2O], had varying amounts of water content and the respective compositions were found to be n = 4 for [(Ni(suc)(H2O)2).2H2O]n, 1, n = 2 for [Co(suc)]n.2H2O, 2 and n = 0 for [Cu(suc)]n, 3. TG analysis could quantify the amount of water present in the various metal succinates. The data obtained are consistent with

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

89

the compositions indicated in the Table 3.1. We find that the water content in each of the metal succinates is the same irrespective of the two preparative procedures employed. Table 3.1. Elemental analytical data of metal(II) succinates
Complex (Emp. formula) [(Ni(suc)(H2O)2).2H2O]n NiC4H12O8 Formula weight Elemental Content (%) obsvd (calcd) C 19.40 (19.45) H 4.86 (4.90) M 23.9 (23.8) Light green

Colour

246.69

1
[(Co(suc)).2H2O]n CoC4H8O6 210.93

2
[Cu(suc)]n CuC4H4O4 179.54

22.80 (22.75)

3.85 (3.82)

28.0 (27.9)

Violet

26.75 (26.73)

2.25 (2.24)

35. 5 (35.4)

Turquoise

Looking at the IR spectra of the succinates, the broad band at 3050 cm-1 due to (O-H) in the free ligand, H2suc was found to be absent in all the metal(II) succinate complexes. This indicates the deprotonated form of succinate in the metal complexes. Broad peaks in the range 3400-3260 cm-1 are seen in the case of Ni(II) and Co(II) complexes whereas no such peak is observed for the corresponding Cu(II) complex. These peaks are characteristic of succinates, the peaks in this H2O (O-H band) and indicate the presence of water in the system. Among the cobalt(II) and nickel(II) range are seen to be more broad for the nickel than for the cobalt complex. The peak centred at 3350 cm-1 in [(Co(suc)).2H2O]n is typical of uncoordinated water and indicates that the complex

90

Chapter 3

contains only lattice water. However, a careful analysis of the (O-H) band in 1 shows peaks at 3260 cm-1, besides broad peak at 3400 cm-1. This shows the presence of coordinated water in the complex in addition to lattice water. The bending mode (O-H) of H2O in Their The typical compounds 1 and 2 are seen in the range 1630-1640 cm-1. librational modes could be located below 600 cm-1.

carboxylate peaks as(CO2) and s(CO2) for the succinic acid are seen to occur at 1690 and 1428 cm-1 respectively. According to the literature the coordination modes of carboxylate groups could be determined by the separation ( ) between as(CO2) and s(CO2).(40-42) Bidentate

chelating carboxylate groups show a smaller separation for (below 200 cm-1) whereas unidentate carboxylate groups show a larger separation (above 200 cm-1).(43,44) For the present metal(II) succinates these two carboxyl peaks are seen to be at 1593, 1410 cm-1 for 1, 1597, 1417 cm-1 for 2 and 1610, 1424 cm-1 for 3 with 183, 180, 186 cm-1 respectively (Table 3.2). The lower values (around 180 cm-1) for the metal(II) succinates compared to 262 cm-1 of succinic acid indicates the symmetric nature of the carboxylate group, suggesting the chelating character of the COO moiety. The C-O stretching frequencies in these complexes are also seen to be in the range 1304-1296 cm-1 which is typical of chelating carboxylate group.

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

91

Table 3.2. IR spectral data of metal(II) succinates (cm-1)

Compound H2suc (O-H) 3050 3400 3350 (O-H) 1610 1630 1640 as(CO2) 1690 1593 1597 1610 s(CO2) 1428 1410 1417 1424 (C-O) 1305 1304 1296 1300 262 183 180 186

1 2 3

It is interesting to note that the order of for the metal(II) succinates is Cu2+ > Ni2+ > Co2+ which is consistent with IrvingWilliams series(45) based on stability of the complexes. The electronic spectra of metal(II) succinates could be recorded only in the solid state because of their high insolubility. The absorption maxima are given in Table 3.3. Nickel(II) succinate, 1 gave three peaks at 25250, 14140 and 10910 cm-1 which are typical of octahedral Ni(II).(46,47) In the case of cobalt(II) succinate, 2 the Co(II) complex due to 4A2 4T1(P) absorption peaks were observed at 17850, 15600 and 13150 cm-1 which are expected for tetrahedral transition.(46-48) The near IR peak expected around 7500 cm-1 for such a complex could not be measured because of the limitation of the instrument employed. The broad absorption band observed for copper(II) succinate, 3 at 14680 cm-1 is characteristic of an almost square planar structure.(49-51)

92

Chapter 3

Table 3.3. Electronic spectral and magnetic data of metal(II) succinates

Compound Absorption max Assignments eff
(BM)

(cm-1)
3A 3A 2g(F) 2g(F) 2g(F)

10910

3T2g(F) 1 3T1g(F) 2 3T1g(P) 3 2.81

14140 25250 17850

3A

15600 13150

4A

4T1(P)

4.10

14680

2B

1g

2A1g

1.50

Magnetic measurements showed that all the above succinate complexes are paramagnetic in nature. The eff value of 2.81 BM for compound 1 rules out the possibility of the normally expected square planar structure for the complex. Consistent with the electronic spectral data of the nickel succinate the magnetic moment data also confirm the octahedral geometry for the complex. The room temperature eff value of the compound 2 was found to be 4.1 BM. Cobalt(II) is a d7 system and has the ability to take either low spin configuration (with one unpaired electron) or high spin state (with three unpaired electrons). In its 4-coordinated form the low spin state should be of square planar geometry and high-spin state of tetrahedral structure. The 6-coordinated form also can have either high-spin or low-spin forms depending on the ligand field strength

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

93

(10 Dq).

Both the electronic spectrum and magnetic moment The magnetic moment of the for typical Cu(II) complexes.

are consistent with the tetrahedral geometry of the succinate complex of the metal ion. than the value expected compound 3 was found to be 1.50 BM which is slightly lower Carboxylate groups are known to act as good bridging moieties for Cu(II) which is manifested in many of their carboxylate complexes including in Cu 2 (CH 3 COO) 4 .2H 2 O. (52,53) Though the observed eff value for 3 is not as low as that observed in copper(II) acetate we expect some extent of Cu-Cu interactions in 3 and the overall structure may be one that favours such interaction function. facilitated by bridging ability of carboxylate All the available data indicated the strict fourBased of the

coordinated character for cobalt(II) and copper(II) succinates and six coordinated character for nickel(II) succinate. on the above observations and high insolubility

succinates the overall structure around the metal centre in the succinate complexes could be considered as polymeric in nature as shown in Scheme 3.1 .

94

Chapter 3

OH2 OH2 O Ni O OH2 C CH2 CH2 C O OH2 O Ni O O C CH2 CH2 C O OH2 O Ni OH2

O O Co O
2

O Co C CH2 O CH2 C O O Co

CH2 C CH2

C O

O O Cu O
3

O Cu C O CH2 CH2 C O O Cu

CH2 C CH2

C O

Scheme 3.1 Tentative structures assigned for 1, 2 and 3.

3.3.2 Lewis-base mediated fragmentation of nickel(II) succinate As indicated in Chapter 1, one of our main aims in the present study is Lewis-base mediated fragmentation of polymeric metal dicarboxylates. Such a fragmentation is anticipated to occur because Lewis-bases being strong electron pair donating ligands can coordinatively saturate the metal ion and can force the chelating/ bridging carboxylate moieties to take up monodentate or ionic form

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

95

because of their highly flexible bonding features.

Consequently,

depending on the nature and stoichiometric proportion of the Lewisbases and also on reaction conditions it is expected that a wide variety of interesting mixed ligand complexes could be generated with no complication caused by any other competing anion other than carboxylate moieties. We have employed the following Lewisbases taking into consideration their relative pKa values and also chelating or monodentate nature (Fig 3.1).
NH2 NH2 en NH2 NH2 N N

1,3- pn

2, 2 I _ bipy

N 1,10- phen

N py

Fig 3.1. The various Lewis-bases used for fragmentation

Being moderately strong ligands they are expected to bring about effective depolymerisation and result in structurally altered fragment species by affecting the ligation features of the carboxylate moieties and also coordination sphere expansion. We have carried out the interaction of Lewis-bases with the metal succinates under various reaction conditions and stoichiometric proportions. However, to isolate the new structural species we have employed some optimum reaction conditions to avoid any possible product mixture. These along with some salient features and products isolated are presented in Table 3.4.

96

Chapter 3

Table 3.4 Interaction of metal succinates with various Lewis-bases (LB)

Metal succinate +LB (in MeOH) 1 + en (1:1) 1 + en (1:2) 1 + bipy (1:1) 1 + bipy (1:2) 1 + phen (1:1) 1 + phen (1:2) 1 + py (1:1) stirring, RT, (2h) stirring, RT, (1h) stirring under reflux, (2h) stirring under reflux, (1h) stirring under reflux, (2h) stirring under reflux, (1h) stirring under reflux, (3h) stirring under reflux, (3h) stirring under reflux, (3h) partial dissolution to give light violet solution complete dissolution (clear violet solution) partial dissolution (light violet solution) complete dissolution (clear light violet solution) partial dissolution (light violet solution) complete dissolution (clear light violet solution no observable change slight colour change from green to light green (incomplete reaction) complete dissolution followed by green solid separation [Ni(H2O)(py)suc]n (7) [Ni(phen)2(H2O)2]suc.2H2O (6) [Ni(bipy)2(H2O)2]suc.2H2O (5) no stoichiometric compound

Conditions

Observation

Products Separated

[Ni(en)2(H2O)2]suc.2H2O

(4)

no characterisable product

no stoichiometric compound

no characterisable product

1 + py (1:2)

no stoichiometric compound

1 + (py excess)

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

97

1 + pn (1:1) 1 + pn (1:2) 2 + en (1:1) 2 + en (1:2) 2 + bipy (1:1) 2 + bipy (1:2) 2 + phen (1:1) 2 + phen (1:2) 2+py (1:1) 2+py (1:2) 2+(py excess) 2 + pn (1:1) 2 + pn (1:2)

stirring, RT, (2h) stirring, RT, (1h) stirring, RT, (2h) stirring, RT, (1h) stirring under reflux, (2h) stirring under reflux, (1h) stirring under reflux, (2h) stirring under reflux, (1h) stirring under reflux, (3h) stirring under reflux, (3h) stirring under reflux, (3h) stirring, RT, (2h) stirring, RT, (1h)

partial dissolution (light violet solution) complete dissolution followed by violet solid separation partial dissolution (light brown solution) complete dissolution (clear dark brown solution) partial dissolution (light brown solution) complete dissolution (clear dark brown solution) partial dissolution (light orange solution) complete dissolution (light orange solution) no observable change slight colour change (from violet to pink) colour change from violet to pink (solution colourless) partial dissolution (light brown solution) complete dissolution (clear dark brown solution)

no characterisable product

[Ni(pn)2suc]n no stoichiometric compound [(Co(en)2(suc)).H2O]n

(8)

(9)

no characterisable product

[Co(bipy)2(H2O)2]suc.2H2O (10)

no characterisable product

[Co(phen)2]suc.2H2O

(11)

no stoichiometric compound no characterisable product

[Co(py)2(suc)]n

(12)

no stoichiometric compound

[(Co(pn)2(suc)).H2O]n

(13)

98

Chapter 3

Metal succinate +LB (in MeOH) 3 + en (1:1)

Conditions

Observation Colour change from blue to violet (solution colourless) complete dissolution (clear dark violet solution) colour change from blue to light blue (incomplete reaction) complete dissolution followed by precipitation of light blue solid colour change from blue to light green (incomplete reaction) complete dissolution (clear green solution) no observable change slight colour change from blue to light green (incomplete reaction) colour change from blue to green (solution colourless)

Products Separated

stirring, RT, (2h)

[Cu(en)suc]n

3 + en (1:2)

stirring, RT, (1h)

[Cu(en)2(H2O)2]suc

(15)

3 + bipy (1:1)

stirring under reflux, (2h)

no stoichiometric compound

3 + bipy (1:2)

stirring under reflux, (1h)

[Cu(bipy)suc]n

(16)

3 + phen (1:1)

stirring under reflux, (2h) stirring under reflux, (1h) stirring under reflux, (3h) stirring under reflux, (3h)

no characterisable product

3 + phen (1:2) 3 + py (1:1)

[Cu2(phen)4suc]suc.12.5H2O (17

no stoichiometric compound

3 + py (1:2)

Product mixture

3+(py excess)

stirring under reflux, (3h)

[Cu(py)2(suc)]n

(18)

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

colour change from blue to dark blue (solution colourless) complete dissolution (clear dark violet solution)

99

3 + pn (1:1)

stirring, RT, (2h)

[Cu(pn)(suc)]n

(19)

3 + pn (1:2)

stirring, RT, (1h)

[Cu(pn)2(H2O)2 ]suc

(20)

While phen, bipy and en are known for bidentate chelating properties, pyridine is a monodentate ligand. These along with their relative donor abilities can be expected to be the factors which determine the course of fragmentation reaction and the nature of the products. Not many pn adducts have been reported and it can be expected that it can act either as a bridging or as a chelating ligand.(54-57) As indicated in Table 3.4 and in the preparative section, adduct formation and breaking up of the polymeric network occur with comparative ease with en, phen and bipy at the addition of the ligand itself. In the case of pn and py, the depolymerisation takes place slowly to give a clear solution from which the solid adduct could be separated on standing. The analytical data shown in Table 3.5 confirm the formation of 1:2 (nickel succinate : Lewis-base) adducts with en, bipy, phen and pn and 1:1 complex for py. Table 3.5. Elemental analytical data of Lewis-base adducts of metal(II) succinates
Formula weight Elemental content % obsvd (calcd) C [Ni(en)2(H2O)2]suc.2H2O (4) NiC8H28O8N4 366.69 26.15 (26.18) H 7.70 (7.69) N 15.30 (15.27) M 15.9 (16.0) Violet

Complex (Emp. formula)

Colour

100

Chapter 3

[Ni(bipy)2(H2O)2]suc.2H2O NiC24H28O8N4 (5) [Ni(phen)2(H2O)2]suc.2H2O NiC28H32O10N4 (6) [Ni(py)(H2O)suc]n NiC9H11O5 N [Ni(pn)2suc]n NiC10H24O4N4 [(Co(en)2suc)H2O]n CoC8H22O5N4

559.01

51.50 (51.51) 52.20 (52.24) 39.71 (39.73) 37.18 (37.15) 3.70 (30.67) 51.50 (51.49) 55.29 (55.31)

5.05 (5.04) 5.02 (5.01) 4.10 (4.07) 7.48 (7.49) 7.10 (7.08) 5.05 (5.04) 4.62 (4.64)

10.05 (10.01) 8.72 (8.70) 5.18 (5.15) 17.32 (17.34) 17.90 (17.89) 10.05 (10.01) 9.20 (9.21)

10.5 (10.4) 9.2 (9.1) 21.6 (21.5) 18.2 (18.1) 18.9 (18.8) 10.6 (10.5) 9.8 (9.7)

Light violet Light violet Bluish green Light violet Light brown Orange brown Orange

643.15

(7)

271.79

(8)

322.95

(9)

312.93

[Co(bipy)2(H2O)2]suc.2H2O CoC24H28O8N4 (10) [Co(phen)2]suc.2H2O CoC28H28O8N4 (11)

559.31

607.39

[Co(py)2suc]n CoC14H14O4N2 [(Co(pn)2suc)H2O]n CoC10H26O5N4 [Cu(en)suc]n CuC6H12O4N2 [Cu(en)2(H2O)2]suc CuC8H24O6N4 [Cu(bipy)suc]n CuC14H12O4N2 [Cu2(phen)4(suc)] suc.12.5H2O Cu2C56H65O20.50N8 [Cu(py)2suc]n CuC14H14O4N2 [Cu(pn)suc]n CuC7H14O4N2 [Cu(pn)2(H2O)2]suc C C H O N

(12)

333.13

50.40 (50.43) 35.20 (35.17 30.08 (30.05) 28.63 (28.61) 50.06 (50.04)

4.25 (4.23) 7.70 (7.68) 5.05 (5.04) 7.24 (7.20) 3.61 (3.61)

8.42 (8.40) 16.45 (16.41) 11.70 (11.68) 16.70 (16.68) 8.35 (8.35)

17.7 (17.6) 17.3 (17.2) 26.6 (26.5) 18.8 (18.9) 18.8 (18.9)

Rose Light brown Light violet Violet Sky blue

(13)

341.19

(14)

239.54

(15)

335.54

(16)

335.73

1305.24 (17) 337.74

51.50. (51.48)

5.03 (5.02)

8.61 (8.58)

9.8 (9.7)

Light green

(18)

49.75 (49.74) 33.13 (33.11) 32.95 (32 98)

4.16 (4.17) 5.55 (5.56) 7.76 (7 75)

8.30 (8.29) 11.05 (11.03) 15.40 (15 39)

18.9 (18.8) 24.9 (25.0) 17.5 (17 4)

Bluish green Dark blue Violet

(19)

253.67 363.80

(20)

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

CuC10H28O6N4 (20) (32.98) (7.75) (15.39) (17.4)

101

3.3.3 IR spectra of Lewis-base adducts of nickel(II) succinate The IR spectra of all the adducts of nickel(II) succinate obtained by the fragmentation process by Lewis-base attack showed the presence of characteristic peaks of the Lewis-bases in them. The peaks due to succinate moiety were also present but with some shift in their position as compared to the values in the parent metal(II) succinate. The as(CO2) stretching band occurring at 1593 cm-1 in [(Ni(suc)(H2O)2).2H2O]n, (1) was found shifted to 1550-1589 cm-1 in its adducts and s(CO2) stretching band observed at 1410 cm-1 was found lowered to 1380-1402 cm-1 in them. Both as(CO2) and s(CO2) stretching values of the monomeric as well as the polymeric adducts were found to be lower than the precursor complex. This lowering could be attributed to the following reasons. Since Lewis-bases are very good electron donors, they would increase electron density on the metal ion through coordination. This would enhance the electron density on the metal ion which can then back-donate its electrons to the carboxylate groups. Such a back donation is possible in -COO moieties because of the existence of empty orbitals in them and this would be always to the antibonding orbital (*) of the carboxylate group. Consequent to the population in the antibonding orbital of the -COO group, the overall bond order in -COO would decrease, resulting in the lowering of both the as(CO2) and s(CO2) stretching frequencies. The spectra of individual adducts are discussed below in detail. Aliphatic primary amines are known to have their as(NH2) vibration in the range 3400-3300 and s(NH2) in the region

102

Chapter 3

3330-3250 cm-1 respectively. The (NH2) are reported to occur in the range 1650-1550 cm-1.(59,60) In the adduct [Ni(en)2(H2O)2]suc.2H2O, 4, the NH2 stretching bands of en were observed at 3360 and 3250 cm-1 and NH2 bending band (NH2) was seen at 1582 cm-1. The as(CO2) and s(CO2) bands of the carboxylate moieties in 4 were observed at 1550 and 1398 cm-1 respectively and the value (152 cm-1) is characteristic of non coordinated carboxylate groups in the complex. Bands, which have been suggested to be most usefully diagnostic of coordination of bipy to a metal ion, are those at 995 and 759 cm-1. The former peak shifts to 1010 cm-1 in its complex(61) and the strong band at 759 cm-1 ( C-H) shifts by 10-20 cm-1 to higher frequency. This reflects the bidentate nature of 2,2'-bipyridyl.(62) The IR spectrum of the adduct [Ni(bipy)2(H2O)2]suc.2H2O, 5, shows new peaks at 774, 1010, 1440 and 1600 cm-1 indicating that bipy are coordinated to Ni through both of its pyridyl N.(63,64) The as(CO2) and s(CO2) bands were observed at 1558 and 1401 cm-1 respectively. The value (157 cm-1) again confirms the non-coordinated character of the carboxylate group. The bands at 648 and 439 cm-1 are due to deformation modes of pyridyl moiety.(65) In the IR spectrum of the complex [Ni(phen)2(H2O)2]suc.2H2O, 6, new peaks were observed at 720, 1424 and 1625 cm-1 indicating that phen are coordinated to Ni through both of their pyridyl N. The peaks at 1555 and 1400 cm-1 are assigned to as(CO2) and s(CO2) respectively ( =155 cm-1) and show that the carboxylate moieties exist in ionic form. Ring deformation modes of phen moiety were observed at 640 and 435 cm-1. The bands at 3230 cm-1 show the

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

103

presence of coordinated water and a weak band at 3400 cm-1 indicates the presence of lattice water. The C=C and C=N ring stretching skeletal bands of pyridine are known to occur in the range 1420-1600 cm-1.(60.66) Upon complex formation the characteristic in-plane ring deformation at 604 cm-1 and out-of-plane ring deformation at 405 cm-1 of free pyridine moiety were seen shifted to higher frequencies. In [Ni(py)(H2O)suc]n, 7, the new bands were found at 1602, 1573, 1438 and 1402 cm-1. The in-plane ring deformation was observed at 678 cm-1 and out-of-plane ring deformation at 433 cm-1. The shifts observed for these bands in the complex formation confirms the coordination of py. The bands at 1573 and 1402 cm-1 are due to the bidentate linkage of the carboxylate group ( =171 cm-1). The peaks at 1602 and 1438 cm-1 were assigned to (C-C) and (C-N) stretching of pyridine moiety. The bands at 3210 and 704 cm-1 indicate the presence of coordinated water. (43) In the IR spectrum of [Ni(pn)2suc]n, 8, the as(NH2) and s(NH2) stretching bands of pn are seen to occur at 3310 and 3278 cm-1 respectively. The (NH2) band was observed at 1560 cm-1. The as(CO2) and s(CO2) bands of the carboxylate moiety were observed at 1589 and 1380 cm-1 respectively. The value (209 cm-1) clearly shows that the carboxylate group is acting as monodentate ligand with the metal.(43,44) All the other relevant IR absorption frequencies of nickel(II) succinate and their adducts are given in Table 3.6. We have monitored the trend in the changes of both asymmetric and symmetric stretching frequencies in the various adducts. The order for (as(CO2)-s(CO2)) among the adducts are

104

Chapter 3

seen to be 8 > 7 > 5 > 6 > 4. This is seen to be commensurate with the combined effect of pKa values of Lewis-bases (10.47 (pn), 9.92 (en), 5.17 (py), 4.85 (phen) and 4.35 (bipy)) and also their chelating abilities.(58) It may be noted that en and pn are entirely -donors and have no -accepting abilities while bipy and phen have some -accepting nature also because of the availability of * orbitals in them. These factors also have to be taken into consideration while comparing the mentioned above. It also have to be borne in mind that no back donation to * orbitals of -COO is possible if the carboxylate moiety exists as ionic species.

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

105

Table 3.6

IR spectral data of nickel(II) succinate and its various Lewis-base adducts (cm-1)
1 3400 3260 1593 1410 183 1304 4 (en) 3405 3240 1550 1398 152 1276 5 (bipy) 3410 3270 1558 1401 157 1300 1600 6 (phen) 3400 3230 1555 1400 155 1292 1625 7 (py) 3210 1573 1402 171 1302 1602 8 (pn) 1589 1380 209 1263 -

Adducts (O-H) as(CO2) s(CO2) (C-O)

C C C N
(C-N) (C-H) (C-H) (NH2) (NH2) NH2 wag MN stret Ring deformation (outplane) (inplane)

1024 3360 3250 1582 659 524

1440 774 1010 -

1424 720 -

1438 -

1015 3310 3278 1560 689 496

439 648

435 640

433 678

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

107

3.3.4

Electronic spectra and magnetic data of Lewis-base adducts of nickel(II) succinate The electronic spectra of all the adducts of nickel(II)

succinate are recorded in solid as well as in liquid (methanol) states. The authenticity of all the peaks in solid state spectra was confirmed by recording the spectra by repeated sample preparations. Some of the spectra are reproduced in Fig.3.2. Octahedral complexes of Ni(II) differ from the square planar ones in their absorption characteristics below 10,000 cm-1 which is not seen in square planar complexes because of their very high crystal field strength. Orgel diagram suggests that six coordinate octahedral Ni(II) complex can have generally three bands in the electronic spectra which originate from the following transitions
3A 2g

3T (F) 2g

1;

3A 2g

3T (F) 1g

2;

3A 2g

3T (P) 1g

3.(46) The

characteristic fine features in the bands of parent nickel(II) succinate, 1, are seen disappearing in all their adducts. On examining the electronic spectra of the adducts it can be seen that all of them have three absorption maxima in the ranges 11160-11960 cm-1, 15570-18760 cm-1 and 25570-27390 cm-1 (Table 3.7). These are very characteristic of octahedral Ni(II) complexes and can be assigned to 1, 2, 3 transitions referred above based on literature data.(46)

108

Chapter 3

(a) [(Ni(suc)(H2O)2).2H2O]n, 1 (b) [Ni(en)2(H2O)2]suc.2H2O, 4 (c) [Ni(bipy)2(H2O)2]suc.2H2O, 5 (d) [Ni(phen)2(H2O)2]suc.2H2O, 6 (e) [Ni(py)(H2O)suc]n, 7 (f) [Ni(pn)2suc]n, 8

Fig 3.2 Electronic spectra of nickel(II) succinate and its Lewis-base adducts

From Orgel diagram and electronic transitions observed for the complexes it was possible to calculate Dq, Racah parameter (B) and the nephelauxetic parameter () for all the octahedral Ni(II) complexes. The parameter is a measure of covalent character and it was evaluated using Eq. 3.1 as a percentage contribution.

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

109

B B' = 100 B

... (3.1)

where B is the Racah parameter for the gaseous ion and B' is the same for the complex. A simpler method(67) is also known for the calculation of the Racah parameter (B) from the absorption frequencies (cm-1) which can be given by

B=

2 + 3 3 1
15

.(3.2)

In the case of octahedral Ni(II), the value of 1 can be directly taken as 10 Dq 1 = 10 Dq .. (3.3)

It is also possible to evaluate 10Dq from 2, 3 and B as

10 Dq =

+ 5B
2 3

.. (3.4)

The nephelauxetic parameter () could be obtained by using the relation =

B(Complex) B(Free ion)

.. (3.5)

where B for free ion = 1041cm-1 It is generally seen that the ratio 2/1 in octahedral Ni(II) complex lies in the range of 1.3-1.6. Table 3.7 gives the calculated Dq

110

Chapter 3

values for the various nickel(II) succinate adducts prepared in the present study along with their B and parameter . The energy ratio evaluated for the complexes are also given in the Table 3.7. The values clearly indicate that all the adducts have octahedral geometry. It is instructive to note that the value Dq of Ni(II) adducts decrease in the order 8 > 4 > 7 > 6 > 5. The trend appears to be dependent on the pKa value of the Lewisbases.(58) Higher the value of pKa, stronger would be the donor power of these Lewis-bases. Among these, pn and py adducts can be expected to be having extended polymeric structures while others, being soluble, can be considered to be essentially monomeric species. The values of monomeric adducts are seen to be generally higher than that of polymeric adducts. This is consistent with the observed trend. The Dq value of the en adduct is seen to be slightly higher than that of bipy or phen adducts. This could be attributed to strong ligating capacity of en as compared to bipy or phen which is evident from the pKa values. Similarly the Dq value of pn adduct is higher than that of py adducts. The pKa value of pn is 10.17 while that of py is 5.17 which implies that pn is more basic and stronger -donor than py. Consequently pn is a better ligand than py which is manifested in the difference in their Dq values. Magnetic susceptibility measurements of all the adducts of nickel(II) succinate were carried out to determine the spin state and structure of the complexes. The eff values calculated for the adducts were seen to be in the range 2.80-3.00 BM (Table 3.7). The values are typical of octahedral Ni(II) complexes with some contribution from spinorbit coupling. It is interesting to note that among the various adducts py and pn derivatives have slightly lower value for the eff as

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

111

compared to the en, bipy and phen adducts. As discussed earlier the former ones have an extended polymeric structure while the latter ones exist in monomeric form. We expect that the extended system have lesser orbital contribution to the magnetic moment than the simple monomeric ones. Table 3.7. Electronic spectral and magnetic moment data of Lewisbase adducts of nickel(II) succinate
Adducts Abs. max

(cm-1)
10910 14140 25250 11620

Assignments* 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3
3A2g

Dq (cm-1)

B (cm-1)

2/1

eff
(BM)

1091

0.54

436.3

1.30

2.81

18760 27390 11160

1162

0.65

751.8

1.61

2.93

18280 26040 11320

1116

0.59

722.9

1.64

2.95

18240 26640 11420

1132

0.62

727.6

1.62

2.97

15570 25570 11960

1142

0.49

457.8

1.36

2.84

17210 26380
*
3A2g

1196

0.46

514.1

1.44

2.88

3T2g(F) (1),

3T1g(F) (2),

3A2g

3T1g(P) (3).

112

Chapter 3

3.3.5 Lewis-base mediated fragmentation of polymeric cobalt(II) succinate As mentioned in section 3.3.1, cobalt(II) succinate complex, 2, has an extended polymeric structure bridged through succinate moieties with a tetrahedral MO4 units as evident from high insolubility and characteristic electronic and magnetic properties. The depolymerisation and coordination expansion of the cobalt(II) succinate was attempted by employing the same set of Lewis-bases used for nickel(II) succinate system. We have carried out the interaction studies under various conditions. Several mixed ligand complexes could be isolated by depolymerisation and coordination sphere expansion of 2. Methanol appears to be the most favourable solvent medium for the reaction. The details are presented in Table 3.4 given earlier. In contrast to nickel(II) succinate, the cobalt(II) succinate exhibits slightly different physical and chemical characteristic features with the Lewis-bases. Unlike in the case of nickel(II) succinate, the pyridine adduct formed for cobalt(II) succinate is of 1:2 composition which is found to be insoluble in all the solvents. While en, pn, bipy and phen Lewis-bases yield 1:2 adducts for both systems, there was found to be noticeable solubility difference for these two metal adducts. The adducts of Ni(II) are highly soluble in water and methanol while in the case of Co(II), only the bipy and the phen adducts are soluble in all the solvents. The other adducts remain insoluble in these solvents. The analytical data of the adducts are given in Table 3.5 earlier and are in conformity with the compositions indicated.

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

113

3.3.6 IR spectra of Lewis-base adducts of cobalt(II) succinate The presence of Lewis-bases in all the adducts are confirmed by their characteristic peaks in the IR spectra. The as(CO2) and s(CO2) stretching bands occurring at 1597 and 1417 cm-1 respectively in compound 2 were found shifted to lower regions 1555-1593 cm-1 and 1378-1405 cm-1 respectively in its adducts. The individual details are discussed below. The IR spectrum of [(Co(en)2suc)H2O]n, 9, gave all peaks characteristic of en in addition to the peaks due to parent complex. The NH2 vibrations are seen to occur at 3370 and 3260 cm-1 which could be assigned to as(NH2) and s(NH2) vibrations respectively. A sharp band at 1052 cm-1 in the complex was assigned to (C-N) stretching and a weak band at 3410 cm-1 showed the presence of lattice water in the complex.(59) The as(CO2) band was observed at 1593 cm1 and s(CO2) band at 1383 cm-1 respectively. The value (210 cm-1) is characteristic of the monodentate linkage of the carboxylate group in them.(43,44) For the adduct [Co(bipy)2(H2O)2]suc.2H2O, 10, new peaks were observed at 764, 1020, 1436 and 1640 cm-1 indicating that bipy are coordinated to Co(II) through both of their pyridyl nitrogens.(68,69) Moreover, the as(CO2) and s(CO2) bands are observed at 1558 and 1405 cm-1 respectively which testify the non-coordinated nature of the carboxylate group ( =153 cm-1). The bands at 652 and 440 cm-1 are ring deformation modes of bipyridyl moiety.(66) The band at 3210 cm-1 shows the presence of coordinated water and a broad shoulder band at 3390 cm-1 indicates the presence of lattice water in it.

114

Chapter 3

In the IR spectrum of the adduct [Co(phen)2]suc.2H2O, 11, new bands were observed at 723, 1424 and 1620 cm-1 indicating that phen are coordinated through both of their pyridyl N. The asymmetric and symmetric bands of -COO- group are observed at 1555 and 1400 cm-1 respectively. The value (155 cm-1) confirms the non coordinated character of the carboxylate group in them. The in-plane and out-of-plane ring deformation modes of phen moiety were seen at 646 and 428 cm-1. The broad band at 3401 cm-1 indicated the presence of lattice water in it. In [Co(py)2suc]n, 12, new bands were observed at 1603, 1575, and 1440 cm-1 compared to 2. The peaks at 1603 and 1440 cm-1 are due to C=C and C=N ring stretching skeletal bands of pyridine. The bands at 1575 and 1398 cm-1 were assigned to as(CO2) and s(CO2) of the carboxylate group. The value (177 cm-1) is

characteristic of the bidentate linkage of the -COO- group. The inplane and out-of-plane ring deformations of pyridine moiety were observed at 704 and 425 cm-1. The shifts observed for these bands (compared to 602 and 405 cm-1 in py) on complex formation indicates the coordination of pyridine moiety. In the IR spectrum of [(Co(pn)2suc).H2O]n, 13, as(NH2) and

s(NH2) were seen to occur at 3320 and 3250 cm-1. The presence of lattice water was seen by the appearance of a broad band at 3404 cm-1. Moreover, the as(CO2) and s(CO2) bands were observed at 1585 and 1378 cm-1 respectively. The value (207 cm-1) shows that the carboxylate groups in this adduct act as monodentate moieties. The relevant absorption frequencies of cobalt(II) succinate and their adducts are given in Table 3.8.

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

115

We have monitored the trend in

among the various

adducts. The order was found to be 9 > 13 > 12 > 11 > 10. As in the other adducts the trend appears to be dependent on the pKa value of the Lewis-bases.(58) Table 3.8 IR spectral data of Lewis-base adducts of cobalt(II) succinate (cm-1)
Complex (O-H) as(CO2) s(CO2) 2 3350 1597 1417 180 1296 9 3410 1593 1383 210 1289 10 3390 3210 1558 1405 153 1292 1640 11 3401 1555 1400 155 1302 1620 12 1575 1398 177 1282 1603 13 3404 1585 1378 207 1290 -

(C-O)

C C C N
(C-N) (C-H) (C-H) (NH2) (NH2) NH2wag MN stret. Ring deformation (outplane) (inplane)

1052 3370 3260 1578 742 588

1436 764 1020 -

1424 723 -

1440 -

1042 3320 3250 1557 760 570

440 652

428 646

425 704

116

Chapter 3

3.3.7

Electronic spectra and magnetic data of Lewis-base adducts of cobalt(II) succinate The electronic spectra of all the adducts of cobalt(II) succinate

were recorded either in solution or in solid state. While the parent tetrahedral complex showed three peaks, the adducts of en, pn, bipy and py showed set of bands around 15000 and 21000 cm-1. These are very characteristic of octahedral Co(II) complexes and could be assigned to 4T1g 4A2g and 4T1g 4T1g(P) transitions respectively.(70) Because of the limited range of the instrument used we could not locate the low energy peak around 9000 cm-1 which is expected for octahedral Co(II) for 4T1g 4T1g(F) transition. The data are tabulated in Table 3.9. Some of the spectra are reproduced in Fig. 3.3. The data indicated that all the adducts of en, pn, bipy and py except the phen adduct are octahedral while the latter is distinctly tetrahedral. Even though there is difference in the peak maximum in these adducts, no attempt was made to determine the relative field strength and other spectroscopic parameters for the adducts. It is known that octahedral Co(II) complexes have eff values in the range 4.3-5.0 BM because of their high-spin nature and also due to higher spin-orbit coupling compared to that in tetrahedral system.(71,72) In our adducts, those of en, pn, bipy and py have values in this range (Table 3.9) indicating that they have octahedral structure. In contrast, the eff value of [Co(phen)2]suc.2H2O, 11, clearly indicates that the compound is tetrahedral in nature.

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

117

Table 3.9

Electronic spectral and magnetic moment data of Lewisbase adducts of cobalt(II) succinate
Abs. max

Adducts

(cm-1)

Assignments

eff
(BM)

17850 2 15600 13150 21920 15550 21640 15820 18450 11 15690 13420 12 20200 15870 21880 15570
4T 1g 4A 2 4T 1g 4A 2

4T1 (P)

4.10

4T1g (P) 4A2g

4T 1g

4.73

10

4T 1g

4T1g (P) 4A2g

4T 1g

4.68

4T1 (p) 4T1g (P) 4A2g

4.31

4T 1g 4T 1g

4.75

13

4T1g (P) 4A2g

4T 1g

4.66

118

Chapter 3

(a) [(Co(suc)).2H2O]n, 2 (b) [(Co(en)2suc)H2O]n, 9 (c) [Co(bipy)2(H2O)2]suc.2H2O, 10 (d) [Co(phen)2]suc.2H2O, 11 (e) [Co(py)2suc]n, 12 (f) [(Co(pn)2suc)H2O]n, 13

Fig. 3.3 Electronic spectra of cobalt(II) succinate and its Lewis-base

adducts 3.3.8 Lewis-base mediated fragmentation of polymeric copper(II) succinate Just as in the case of nickel(II) succinate and cobalt(II) succinate, adduct formation studies have been investigated with copper(II) succinate also with the same set of ligands. The interaction was studied in various reaction conditions and also by changing the stoichiometric ratio of the parent succinate and Lewis-bases. As

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

119

indicated in the preparative section and also referred in Table 3.4, the depolymerisation and adduct formation occur with comparative ease with en, pn and phen at the addition of the ligand itself (1:2 ratio). In the case of bipy, there is some indication of 1:1 adduct formation but the compound could not be isolated in pure form. However, the addition of bipy in the ratio 1:2 yielded a clear solution from which solid was found to be thrown out which could be analysed for 1:1 (complex: Lewis-base) composition rather than 1:2. Our efforts show that no 1:2 adduct could be isolated for bipy system unlike in the other adducts. In the case of en and pn, unlike in cobalt(II) and nickel(II) succinate, copper(II) succinate yielded 1:1 adducts also. Similar to cobalt(II) succinate, copper(II) succinate yielded 1:2 adduct with pyridine. The analytical data shown in Table 3.5 confirm the given composition for the above adducts of copper(II) succinate. 3.3.9 IR spectra of Lewis-base adducts of copper(II) succinate As compared to the IR spectrum of copper(II) succinate, its Lewis-base adducts gave several additional and modified peaks. The important IR vibrations are presented in Table 3.10 along with their assignments. The new peaks in all the cases correspond to those of the Lewis-base moiety present in each of the complex. The as(CO2) band occurring at 1610 cm-1 in parent copper(II) succinate, 3, was found shifted to 1550-1596 cm-1 in its adducts. Similarly the as(CO2) band observed at 1424 cm-1 was seen shifted to 1390-1422 cm-1 in the adducts. The spectra of individual adducts are discussed below in detail. In the IR spectrum of the adduct [Cu(en)suc]n, 14, the NH2 vibrations were observed at 3280 cm-1 (as) and 3240 cm-1 (s) while the

120

Chapter 3

bending mode (NH2) was found to be at 1630 cm-1. The as(CO2) and s(CO2) bands were found to be at 1596 and 1422 cm-1 respectively. The value (174 cm-1) gave a clear indication that the carboxylate group is bonded to the metal in a bidentate fashion.(40-42) The IR spectrum of the adduct [Cu(en)2(H2O)2]suc, 15, gave all peaks characteristic of en in addition to the parent peaks. The as(NH2) and s(NH2) vibrations are seen to occur at 3300 and 3200 cm-1 respectively. The bending mode (NH2) was seen at 1580 cm-1 The strong band at 1040 cm-1 could be assigned to (CN) stretching. Moreover, the as(CO2) and s(CO2) bands were observed at 1555 and 1399 cm-1 respectively with a value of 156 cm-1

indicating that the carboxylate function exists as ionic species. The IR spectrum of the adduct [Cu(bipy)suc]n, 16, shows new peaks at 780, 1030, 1460 and 1600 cm-1 indicating that bipy is coordinated to Cu through its pyridyl nitrogen.(73,74) A weak absorption peak at 1258 cm-1 and the insoluble nature of the complex in almost all organic solvents suggest a polymeric structure for the complex. The as(CO2) and s(CO2) were observed at 1580 and 1401 cm-1 respectively. The value of 179 cm-1 clearly shows that the

succinate group acts as bidentate moiety. Ring deformation modes of bipy were seen at 635 and 422 cm-1. In the IR spectrum of [Cu2(phen)4(suc)]suc.12.5H2O, 17, new bands were found at 720, 1500 and 1625 cm-1 indicating that phen are coordinated to Cu through both of its pyridyl N. In addition to these bands, new peaks were seen at 1605, 1558,1421 and 1400 cm-1 which indicate the presence of both chelating -COO- (1605, 1421 cm-1

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

121

with = 184 cm-1) and ionic -COO- (1558, 1400 cm-1 with = 158 cm-1) moieties in the adduct.(40-44) The bands at 670 and 425 cm-1 are ring deformation modes of phen moiety. The strong and broad absorption band centred around 3400 cm-1 is indicative of lattice water. In [Cu(py)2suc], 18, the peaks at 1630 and 1480 cm-1 were assigned to C=C and C=N ring stretching skeletal bands of pyridine and those at 1595 and 1420 cm-1 to as(CO2) and s(CO2) of the carboxylate moiety respectively. The value (175 cm-1) confirms the bidentate chelation of the carboxylate group with Cu2+ ion. The in-plane and out-of-plane ring deformation modes of pyridine moiety were seen at 700 and 420 cm-1 respectively. The shifts observed for these bands on complex formation indicates the coordination of pyridine moiety to the metal through its nitrogen. In the IR spectrum of [Cu(pn)suc]n, 19, the as(NH2) and s(NH2) vibrations of pn were observed at 3290 and 3250 cm-1 and the bending mode (NH2) at 1605 cm-1. The peak at 1034 cm-1 could be assigned to (CN) stretching. The as(CO2) and s(CO2) stretching bands were observed at 1579 and 1403 cm-1 respectively. The value (176 cm-1) shows that the carboxylate groups are bidentate in nature. For the adduct [Cu(pn)2(H2O)2]suc, 20, the as(NH2) and s(NH2) vibrations of pn were found at 3325 and 3288 cm-1 while the bending mode (NH2) was observed at 1602 cm-1. The peak at 1025 cm-1 could be assigned to (CN) stretching. The as(CO2) and s(CO2) bands were observed at 1550, 1398 cm-1 respectively. The appearance of a stronger band at 3200 cm-1 indicates the presence of coordinated water.

122

Chapter 3

We have also monitored the trend in among the various adducts. The order was found to be 17 > 16 > 19 > 18 > 14 > 15 > 20. As in the other adducts the trend appears to be dependent on the pKa value of the various Lewis-bases.(58) Table 3.10 IR spectral data of Lewis-base adducts of copper(II) succinate (cm-1)
Adducts (O-H) as(CO2) s(CO2) (C-O) 3 1610 1424 186 1300 14 1596 1422 174 1292 15 3220 1555 1399 156 1280 16 1580 1401 179 1278 1600 17 3400 1605 1558 1421 1400 184 158 1270 1625 18 1595 1420 175 1290 1630 19 1579 1403 176 1283 20 3200 1550 1398 152 1265 -

C C C N
(C-N) (C-H) (C-H) (NH2) (NH2) NH2wag MN stret. Ring deformation (outplane) (inplane)

1040 3280 3240 1630 720 600

1040 3300 3200 1580 640 522

1460 780 1030 -

1500 720 -

1480 -

1034 3290 3250 1605 498

1025 3325 3288 1602 659 515

422 635

425 670

420 700

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

123

3.3.10

Electronic spectra and magnetic data of Lewis-base adducts of copper(II) succinate

The electronic spectra of various adducts of copper(II) succinate were recorded either in solid state or in solution and are shown in Fig. 3.4-3.5. The data are presented in Table 3.11 along with their assignments. The authenticity of all the peaks was confirmed by recording the spectra by repeated sample preparation.

(a) [Cu(suc)]n, 3 (b) [Cu(en)suc]n, 14 (c) [Cu(bipy)suc]n, 16 (d) [Cu(py)2suc]n, 18 (e) [Cu(pn)suc]n, 19

Fig 3.4.

Electronic spectra of copper(II) succinate and its polymeric adducts

124

Chapter 3

Tetragonal copper(II) complex are expected to show the transition 2B1g 2A1g, 2B1g B2g and 2B1g 2Eg. But bands due to
B B B

these transitions usually overlap to give one broad absorption band.(75,76) In all the adducts generated in the present study a broad band is seen to occur in the region 14810-17480 cm-1 indicating a tetragonal configuration around copper(II) ion.(76) The spectrum of 17, in solution state gave a broad band at 14920 cm-1 besides a shoulder peak at 14080 cm-1. This indicates the presence of two species which could be possibly due to the solvolytic cleavage of the complex. Moreover both n* and * bands due to ligand based transitions were found as blue shifted and appearing in the region 33330-34010 cm-1 and 40160-41840 cm-1 respectively when compared to that of the parent complex. The a1g b1g* transition is found to occur at higher energy for en adduct 15, in comparison with other adducts. The reason could be accounted as follows. On forming the adduct [Cu(en)2(H2O)2]suc, the coordinated succinate moiety in the precursor complex [Cu(suc)]n is replaced by the en ligating group which causes greater ligand field splitting in the complex whereby b1g* orbital gets pushed up higher thereby increasing the a1g b1g* energy gap. Further, the electronic spectra of all the complexes exhibit an intense absorption band in the region 25640-27470 cm1 which could be due to charge transfer transitions. The charge-transfer band for the adduct 17 in solid state was found to be at 26310 cm-1. In solution state, besides the 26310 cm-1 band, additional peak was seen at 23810 cm-1 as a shoulder indicating the presence of two complex species.

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

125

Fig 3.5. Electronic spectra of monomeric adducts of copper(II) succinate (a) (c) [Cu(en)2(H2O)2]suc, 15 (b) [Cu(pn)2(H2O)2]suc, 20

[Cu2(phen)4(suc)]suc.12.5H2O, 17

The magnetic moment values of the various copper(II) succinate complexes vary in the range 1.63-1.79 BM (Table 3.11). Slightly higher eff values observed for monomeric adducts compared to the spin only value of 1.73 BM could be due to some orbital contribution.(77) The magnetic moment values of the dimeric as well as the polymeric adducts are lower than the value expected for one unpaired electron, indicating the possibility of some metalmetal interaction.(78)

126

Chapter 3

Table 3.11.

Electronic spectral and magnetic moment data of Lewis-base adducts of copper(II) succinate
Abs.max (cm-1) 40000 33220 25310 14680 40480 33550 25640 16720 41150 33440 26380 17480 40320 34010 25700 15430 41660 33670 26310 14920 40650 34010 26520 14810 40160 33440 26450 16500 40980 33330 27470 17210 Assignments * n* Charge transfer 2B 2A 1g 1g * n* Charge transfer 2B 2A 1g 1g * n* Charge transfer 2B 2A 1g 1g * n* Charge transfer 2B 2A 1g 1g * n* Charge transfer 2B 2A 1g 1g * n* Charge transfer 2B 2A 1g 1g * n* Charge transfer 2B 2A 1g 1g * n* Charge transfer 2B 2A 1g 1g eff
(BM)

Adducts

1.50

14

1.66

15

1.79

16

1.68

17

1.65

18

1.63

19

1.67

20

1.78

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

127

3.3.11

EPR Spectra of Lewis-base adducts of copper(II) succinate

In Chapter 2 we have discussed the significance of various spinHamiltonian parameters and the relevant equations involving them. Structural information that can be gathered from these parameters has also been discussed. Some mention has also been made about the inference that can be obtained about the nature of bonding in complexes of Cu(II). It is worthy to mention here some additional relevant points on bonding features that can be obtained from EPR, before we discuss the data in particular. A satisfactory agreement between the ligand field transition and magnetic parameters could be explained by assuming covalent bonding between metal ions and the ligands. By group theoretical approach the proper linear combinations of the ligand orbitals can be combined with the copper d orbitals to form the following antibonding wavefunctions.(79) While the electrons in the bonding functions are essentially those of ligand and electrons, the electrons in the following antibonding functions are mainly metal d electrons. B1g = dx2 - y21/2 2[-x(1)+y(2)+x(3)-y(4)]
B

B2g =dxy-1/2 (1-2)1/2[py(1)+px(2)-py(3)-py(4)]

B

A1g = dz2-21/2(1-2) [x(1)+y(2)+x(3)-y(4)] Eg = dxz-(1-2)1/2[pz(1)-pz(3)/ 2 = dyz-(1-2)1/2[pz(2)-pz(4)/ 2

128

Chapter 3

The wave functions are written in the order of increasing energy. Often the highest among all these orbitals is B1g, which has
B

major contribution from metal-based dx2-y2 orbital. Consequently the unpaired electron can be considered to be residing on dx2-y2 orbital. The B1g and A1g states account for bonding to Cu, the B2g
B

state represents in-plane -bonding and Eg states represent out-ofplane -bonding. The coefficient , , or are related to the covalent character of respective bonds. The smaller the value of these parameters the more covalent the bond associated with them. The bonding parameter (2Cu) of the Cu(II) complexes which is a measure of the covalency of the inplane bonding of the Cu-N bond was calculated by the expression given by Kivelson and Neiman.(80,81) The equation is based on the copper hyperfine tensor A as 2Cu = -(A /0.036) + (g-2.002) + 3/7(g-2.002) + 0.04 For covalent bonding, 2Cu is usually between 0.50 to 0.80 and for ionic type it approaches 1. As 2Cu is inversely related to the -covalency of the Cu-N bond, the compounds which have low value for 2Cu can be considered to have better Cu-N bond. The g values are related to the axial symmetry parameter, G, by the expression G=

g || 2 g 2

, where G can be considered as the measure of the extent of

exchange interaction between Cu centers in the complexes. If G>4, exchange interaction is considered negligible but if G<4, considerable exchange interaction can be expected in the solid state complexes. X band EPR spectra of various Cu(II) succinate complexes were recorded either in solid state or in solution state (1:1 toluene methanol mixture) at liquid nitrogen temperature. The EPR traces

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

129

are presented in Fig.3.6-3.8. Various spin-Hamiltonian parameters were calculated from the spectra using DPPH free radical as the g marker and employing the reported procedure.(79) Some of the adducts have a well resolved g and a broadened g region. In all the spectra, no nitrogen super hyperfine splitting from the ligand is observed. The trend g>g>2.0023 observed for these complexes show that the unpaired electron is localised in the dx2-y2 orbital.(82) The spectrum of insoluble Cu(suc) gave only a broad featureless peak in solid state. To avoid the observed dipolar broadening, diamagnetic dilution of Cu(suc) was carried out in zinc(II) succinate lattice. Cu(suc) doped in Zn(suc) (5 : 95 mole ratio) was prepared by precipitating the metal ions as insoluble succinate complex from their Cu2+ using sodium succinate and by adjusting the pH. The spectrum of 15, 17, 20 were measured in solution form at 77K. Interestingly the spectrum of 17 indicates the presence of two magnetic species with hyperfine splitting shown in Fig.3.8. The spectra could be analysed assuming axial symmetry and as per standard procedure.(79) The spin Hamiltonian parameters could be calculated for both the species of 17 observed in the solution state. The value for species I are A = 165 G, A = 40 G, g = 2.18, g = 2.06, giso = 2.10, G = 3.00 and 2Cu = 0.7007. For species II, the values are A = 160 G, A = 46.7 G, g = 2.26, g = 2.05, giso = 2.12, G = 5.2 and 2Cu = 0.7625. The parameters giso and 2Cu were evaluated by procedures mentioned in Chapter 2. All the relevant spin-Hamiltonian parameters and G values are typical of Cu(II) complexes with tetragonal geometry with dx2-y2 ground state for 17. We expect that species I in 17 is the original dimeric compound (see the crystal structure discussed in section 3.3.12) while species II could be the monomeric complex generated by solvolytic cleavage of

130

Chapter 3

the dimer in solution. The various parameters calculated for all the copper(II) adducts isolated are given in Table 3.12.

Fig. 3.6

EPR spectra of copper(II) succinate and its polymeric adducts in solid state: (a) [Cu(suc)]n, 3 (b) [Cu(en)suc]n, 14 (c) Cu(bipy)suc]n, 16 (d) [Cu(py)2suc]n, 18 (e) [Cu(pn)suc]n, 19

Fig.3.7 EPR spectra of monomeric adducts of copper(II) succinate in toluene-methanol mixture at 77 K: (a) [Cu(en)2(H2O)2]suc,15 (b) [Cu(pn)2(H2O)2]suc, 20

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

131

Fig 3.8 The EPR Spectrum of [Cu2(phen)4suc]suc12.5 H2O, 17 in toluenemethanol mixture at 77 K

Table 3.12 EPR spin-Hamiltonian parameters of copper(II) succinate and its various adducts
Complex [Cu(suc)]n [Cu(en)suc]n [Cu(en)2(H2O)2]suc 15 [Cu(bipy)suc]n [Cu2(phen)4 suc]suc.12.5H2O 17 (I) (II) [Cu(py)2suc]n [Cu(pn)suc]n 18 19 165 160 180 40 46.7 50 2.18 2.26 2.20 2.18 2.22 2.06 2.05 2.08 2.06 2.04 2.10 2.12 2.12 2.10 2.10 0.7007 0.7625 0.7739 3.00 5.20 2.50 3.00 5.50 16 3 14 A (gauss) 130 190 A (gauss) 43.33 53.33 g 2.30 2.19 2.24 2.21 g 2.09 2.07 2.04 2.07 giso 2.16 2.11 2.11 2.12 2Cu 0.7363 0.7850 G 3.33 2.71 6.00 3.00

[Cu(pn)2(H2O)2]suc 20

132

Chapter 3

The A value of the parent complex, copper(II) succinate, 3, is found to be low which indicates that metal d electron is highly delocalised possibly due to bridging through succinate moiety as in copper(II) acetate systems. However, for en adduct 15, pn adduct 20 and phen adduct 17, the A values are comparatively high at 190 G, 180 G and 165 G respectively. The evaluated 2Cu values of these are 0.7850 (15), 0.7739 (20) and 0.7007 (17). This implies that the delocalisation of electron spin decreases in the order 15 >20 > 17, while the -covalency increases in the order 15 < 20 < 17. The above trends can be explained on the following grounds. The chelating en and pn are purely -donors and would function as only electron pair donors. Therefore the unpaired electron does not have any chance to get delocalised onto the ligand framework unless the carboxylate moiety gets bonded in chelating form. Because of the prominent residence of the free electron onto the Cu dx2-y2 orbital the hyperfine constant A appears comparatively high. In the case of phen, bipy and py the Lewis-bases have considerable -acceptor property because of low-lying * orbitals. Therefore they are generally considered as -donor and -acceptor ligands. While the -donor ability of these ligands would accumulate electron density onto the metal, the -acceptor ability would make them accept electron from the metal via backdonation. This would result in appreciable spin-delocalisation from the metal to the ligand. The consequence of this would be the low value for A which is what we find in the phen adduct 17. Since the adducts 14, 16, 18 and 19 are polymeric and insoluble in almost all solvents we could not get any resolved spectra to look at the anisotropic parameters. Overall trend observed for A in the order and that observed for 2Cu in the order agree well with our

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

133

above arguments.

The G values, the measure of the exchange

interaction, show that the adducts 15, 20 and 17(II) remain as isolated molecular entity without any exchange interaction (G > 4). However, in the case of the adducts 14, 16, 18 and 19, we expect appreciable exchange interaction because of the low G values (G < 4). 3.3.12 Crystal and Molecular structure

It has been our interest to study crystal and molecular structure of the various adducts that have been prepared. Even though we could see that most of the components give crystalline solids, only 17 yielded crystals of good quality suitable enough to study the structure. The crystal structure analysis was carried out using an automated Enraf-Nonius CAD4 diffractometer. It shows that the complex 17 crystallizes in the triclinic space group P-I (No.2) with a =12.968(3) , b =14.420(3) , c =17.970(4) ,

= 75.13(3), = 75.13(3), = 69.21(3), V = 2902.2(11) 3, Z = 2,

Dc=1.494g/cm3. Cell dimensions and intensity data were measured at room temperature fitted with graphite-monochromated Mo-K radiation, = 0.71073 . A total of 11372 reflections in the range 2.10-25.970 were collected using scans and after satisfying the I 2(I) criterion of observability 5522 reflections were used in the subsequent structure determination and refinement. The semiempirical absorption was applied. The structure was solved and refined using the SHELXL-97 programme package.(83) The final R indices are 0.1821 and 0.1058 for all observed reflections. Maximum and minimum peaks in the final difference Fourier synthesis are 0.39 and -0.40 respectively.

134

Chapter 3

The crystal structure consists of dinuclear complex cations is shown in Fig. 3.9 and the molecular packing diagram is shown in Fig.3.10. The crystallographic data is listed in Table 3.13, the bond distances and angles are given in the Table 3.14. Each of the Cu2+ ions in the dimeric complex is seen to be surrounded by two O atoms of one of the carboxylate moieties of the succinate ligand and four N atoms of two phen ligands, resulting in a strongly distorted octahedral coordination around Cu with d(Cu-O) = 2.123-2.532 and d(Cu-N) = 1.981-2.144 . The succinato group bis-bidentately bridges the two Cu ions to form dinuclear [(phen)2Cu(-suc) Cu(phen)2]2+ complex cations. The resulting dimeric complex cations, nonconducting succinate anions and water molecules build up the crystal structure. Fig. 3.11 displays an interesting arrangement of the complex cations in the (101) plane. Each complex cation has six neighbors and the void space between two chelating phen planes within the cation is filled with two phen ligands of different neighboring cations. Such an arrangement may have to do with - stacking interactions, since the interplanar phen-phen distances are seen to be in the range 3.31 -3.88 . Based on such effective - stacking interactions, the divalent cations are assembled into positively charged 2D layers, between which the negatively charged hydrogen bonded 2D network formed by the noncoordinating succinate anions and water molecules are sandwiched (Fig.3.10). In addition, the hydrogen bonds reinforce the connection between the positively and negatively charged layers. It is instructive to look at the Cu-Cu distances within the dimeric unit (intra-dimer) and those between neighbouring units (inter-dimer) which are 9.148 for Cu1-Cu1 intra dimer, 5.272 and 9.121 for Cu1-Cu1 inter-dimer and 9.281 for Cu2-Cu2

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

135

inter-dimer, respectively (Fig. 3.11). One of the Cu1-Cu1 interdimer distances, 5.272, is comparatively shorter than others and this can be considered to have some Cu-Cu interaction causing some reduction in its paramagnetic property. The observed eff value of 1.65 BM which is slightly lower than the expected spinonly value, testifies such an interaction. Table 3.13. Crystallographic Data
Molecular formula Molecular weight Color and habit Crystal size Crystal system Space group Unit cell parameters C56H65Cu2N8O20.50 1305.24 Transparent light-green , column-like 0.40 0.15 0.05 mm3 Triclinic P-1 (No.2) a = 12.968(3) b = 14.420(3) c = 17.970(4) V = 2902.2(11) 3 F(000) Density (calcd) Diffractometer Radiation Refs. Used for cell measurement Standard reflections Intensity variation Absorption coefficient Transmission factor Scan type and rate 1358 1.494 g/cm3 Enraf-Nonius CAD4 Graphite-monochromatized Mo K = 0.71073 25, 4.51 11.31 (-2, -3, -3); (-2, -2, -4); (0, 0, -4) 2.5 % 0.818 mm-1 0.879 1.000 scan = 75.13(3)

= 75.13(3) = 69.21(3)
Z=2

136

Chapter 3

Scan range Data collection range Rint (from merging of eqiv. refls.) Reflections measured Total: Unique (n): Observed [I

(0.80+ 0.35 tan ) 0 h 16; -17 k 17; -22 l 22; 2.10 25.97 None

11372 11372 5522 881 None w = 1/2[Fo2+(0.025P)2+1.0 P] 0.1821 (all data) 0.1058 (all data) 1.125 0.00, 0.00 +0.39 to -0.40 e -3 P = (Fo2 + 2Fc2)/3

2(I)]:

No. of variables, p Extinction coefficient Weighting scheme R1 a wR2b Goof (S)c Largest and mean / Largest peak and hole

0.05555 (observed data) 0.0898 (observed data)

aR1 =

|| Fo || Fc || , | Fo |

bwR2 =

[ w( Fo2 Fc2 ) 2 ] , w( Fo2 ) 2

cGoof

=S=

[ w( Fo2 Fc2 ) 2 ] n- p

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

137

Table 3.14. Selected Bond Lengths () and Bond angles (o)

Cu(1)-N(4) Cu(1)-N(1) Cu(1)-N(3) Cu(1)-O(1) Cu(1)-N(2) Cu(1)-O(2) N(4)-Cu(1)-N(1) N(4)-Cu(1)-N(3) N(1)-Cu(1)-N(3) N(4)-Cu(1)-O(1) N(1)-Cu(1)-O(1) N(3)-Cu(1)-O(1) N(4)-Cu(1)-N(2) N(1)-Cu(1)-N(2) N(3)-Cu(1)-N(2) O(1)-Cu(1)-N(2) N(4)-Cu(1)-O(2) N(1)-Cu(1)-O(2) N(3)-Cu(1)-O(2) O(1)-Cu(1)-O(2) N(2)-Cu(1)-O(2) 1.984(3) 1.987(3) 2.074(3) 2.123(3) 2.144(4) 2.532(4) 179.09(16) 81.45(13) 98.08(14) 88.48(13) 91.48(13) 145.49(13) 100.52(14) 80.39(15) 122.68(13) 91.54(13) 90.99(12) 88.25(13) 92.42(12) 54.64(11) 144.15(12) Cu(2)-N(8) Cu(2)-N(5) Cu(2)-N(6) Cu(2)-N(7) Cu(2)-O(3) Cu(2)-O(4) N(8)-Cu(2)-N(5) N(8)-Cu(2)-N(6) N(5)-Cu(2)-N(6) N(8)-Cu(2)-N(7) N(5)-Cu(2)-N(7) N(6)-Cu(2)-N(7) N(8)-Cu(2)-O(3) N(5)-Cu(2)-O(3) N(6)-Cu(2)-O(3) N(7)-Cu(2)-O(3) N(8)-Cu(2)-O(4) N(5)-Cu(2)-O(4) N(6)-Cu(2)-O(4) N(7)-Cu(2)-O(4) O(3)-Cu(2)-O(4) 1.981(3) 1.989(3) 2.080(3) 2.117(4) 2.188(4) 2.442(4) 177.97(14) 99.46(14) 81.17(14) 80.79(14) 100.38(14) 127.45(13) 89.70(13) 88.65(13) 142.46(14) 89.84(14) 88.18(13) 89.91(13) 88.86(13) 143.21(13) 54.89(13)

138

Chapter 3

Fig.3.9. Ortep view of the dinuclear [(phen)2Cu(-L)Cu(phen)2]2+ complex cation with displacement ellipsoids (45% probability) and atomic labelling.

Fig. 3.10 Molecular packing diagram of complex 17 along (101)

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

139

Fig.3.11 The supramolecular assembly of the dinuclear [(phen)2Cu(L)Cu(phen)2]2+ complex cations in to a 2D layer on the basis of the intermolecular - stacking interactions (H atoms are omitted)

For those adducts whose crystal structure could not be solved, some tentative molecular structure could be assigned, based on their composition, IR, electronic, EPR spectral data and also magnetic data. These are summarized below in structural representation I-IX.

N N

OH2 M OH2
I

N N

suc

[M(L)2(H2O)2]suc. [L = (

N = en, bipy, phen; M = Ni(II)] for 4, 5, 6 N

140

Chapter 3

N Ni

O C CH2

CH2

OH2 O

O N O O C CH2 Ni C C O CH O OH2 2 O

N Ni OH2

II
[Ni(py)(H2O)suc]n 7
O O O C N N C O M O N N C O O C O
O C O O N N C O M O N N .H2O C O O C O

III [M(L)2(suc)]n for 8 [M = Ni(II), L = ( = pn]

N N

IV [(Co(L)2suc).H2O]n for 9, 13 [M = Co(II); L = (

N = en, pn] N

N M N

O C O CH2

CH2

O N M O N

O C O CH2 CH2 C O O N M N

V
[M(py)2suc]n [M = Co(II), Cu(II);
N

= py] for 12, 18

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

141

N N

Co

N N

suc . 2 H2O

N N

OH2 Co OH2

N N

suc . 2 H2O

VI
[Co(phen)2]suc.2H2O for 11 N ( = phen. N

VII
[Co(bipy)2(H2O)2]suc.2H2O for 10 N ( = bipy N

N N

OH2 M OH2

N N

suc

N M O C O

N N O O M C O O

N O O

N M

VIII [M(L)2(H2O)2]suc for 15, 20 [M = Cu(II); L = (

N = en, pn] N

IX [M(L)suc]n for 14, 19 and 16 [M = Cu(II); L = (

N = en, pn and N

bipy]

142

Chapter 3

References 1. 2. 3. 4. R. C. Mehrotra and R. Bohra, Metal Carboxylates, Academic Press, New York, (1983) Sir, Geoffery Wilkinson, Comprehensive Chemistry, Vol. 2 (1987) 962 Coordination

C. N. R. Rao, S. Natarajan and R. Vaidhyanathan, Angew. Chem. Int. Ed; 43 (2004) 1466 (a) J. Kim, B. L Chen, T. M. Reineke, H. L. Li, M. Eddaoudi, D. B. Molar, M. O Keeffe and O. M. Yaghi, J. Am. Chem. Soc; 123 (2001) 8239

(b) N. L. Rosi, M. Eddaoudi, J. Kim, M. O Keeffe and O. M. Yaghi, Angew. Chem. Int. Ed; 41 (2002) 284 5.

J. Y. Lu, M. A. Lawandy and J. Li, Inorg. Chem; 38 (1999) 2695 J. Y. Lu, B.R. Cabrera, R.J. Wang and J. Li, Inorg. Chem; 37 (1998) 4480
B. H. O Connor and E. N. Maslen, Acta Crystallogr; 20 (1966) 824 Y. Q. Zheng, J. Sun and J. L. Lin, Z. Anorg. Allg. Chem; 626 (2000) 1718 (a) Y. Q. Zheng, J. L. Lin, J. Sun and H. L. Zhang, Z. Kristallogr. NCS; 215 (2000) 535 (b) Y. Q. Zheng, S. Q. Zhou and J. L. Lin, Z. Kristallogr. NCS; 216 (2001) 265 (c ) Y. Q. Zheng, A. Y. Pan and J. L. Lin, Z. Kristallogr. NCS; 216 (2001) 267

6.
7. 8. 9.

10.

M. P. Gupta, R. D. Sahu, R. Ram and P. R. Maulik, Z. Kristallogr. NCS; 163 (1983) 155

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

143

11. 12. 13. 14. 15.

Y. Q. Zheng and J. L. Lin, Z. Kristallogr. NCS; 215(2000) 157 M. Fleck, E. Tillmanns and L. Bohaty, Z. Kristallogr. NCS; 215(2000) 429 M. Fleck, E. Tillmanns and L. Bohaty, Z Kristallogr. NCS; 215(2000) 619 E. A. H. Griffith, N. G. Charles and E. L. Amma, Acta Crystallogr; B38 (1982) 262 (a) Y. Q. Zheng and J. L. Lin, Z. Kristallogr. NCS; 216 (2001) 139 (b) Y. Q. Zheng, J. L. Lin and W. J. Chen, Z. Kristallogr. NCS; 216 (2001) 269

16. 17. 18. 19. 20.

E. V. Brusau, J. C. Pedregosa and G. E. Narda, J. Solid State. Chem; 153 (2000) 1 C. Livage, C. Egger, M. Nogues and G. Ferey, J. Mater. Chem; 8 (1998) 2743 C. Livage, C. Egger and G. Ferey, Chem. Mater; 11 (1999) 1546 C. Livage, C. Egger and G. Ferey, Chem. Mater; 13 (2001) 410 (a) Y. Kim, E. W. Lee and (2001) 2684 D. Y. Jung, Chem. Mater; 13

(b) Y. Kim and D. Y. Jung, Bull. Korean Chem. Soc; 21 (2000) 656 (c) Y. Kim and D. Y. Jung, Bull. Korean Chem. Soc; 20 (1999) 827

(d) Y. Kim, E. W. Lee and D. Y. Jung, Inorg. Chem; 41 (2002) 501 (e) 21. Y. J. Kim and D. Y. Jung, Inorg. Chem; 39 (2000) 1470

B. N. Figgis and D. J. Martin, Inorg. Chem; 5 (1966) 100

144

Chapter 3

22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35.

R. Vidhyanathan, S. Natarajan Inorg. Chem; 41 (2002) 5226

and

C.

N.

R.

Rao,

P. M. Forster and A. K. Cheetham, Angew. Chem. Int. Ed; 41 (2002) 457 Y. Q. Zheng, W. H. Liu and J. L. Lin, Z. Anorg. Allg. Chem; 628 (2002) 620 J. Yao, Y. L. Fu, S. L. Zheng and X. M. Chen, Main Group Metal Chem; 24 (2001) 289 S. Kawata, S. Kitagawa, M. Enomoto, H. Kumagai and M. Katada, Inorg. Chim. Acta; 288 (1998) 80 H. X. Zhang, B. S. Kang, Z. Y. Zhou, K. B. Yu, Z. N. Chen and C. Ren, Inorg. Chem. Commun; 4 (2001) 695 M. J. Plater, M. Foreman and R. A. Howie, J. Chem. Cryst; 30 (2000) 445 Y. Liu, C. G. Zhang, D. J. Xu and Y. Z. Xu, J. Coord. Chem; 53 (2001) 47 V. T. Yilmaz, S. Demir, O. Andac and W. T. A. Harrison, J. Coord. Chem; 55 (2002) 863 R. Vidhyanathan, S. Natarajan and C. N. R. Rao, Cryst. Growth Des; 3 (2003) 47 Y. Q. Zheng, J. L. Lin and J. Sun, Z. Kristallogr. NCS; 215 (2000) 533 L. S. Long, P. J. Wang, X. Y. Chen and X. M. Fang, Acta Cryst; E57 (2001) M328 Vogels Text Book of Practical Organic Chemistry; IVth Ed. ELBS, London (1978) J. R. Allan and B. R. Carson, Thermochim. Acta; 158 (1990) 91

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

145

36. 37. 38. 39. 40. 41. 42.

Vogels Text Book of Quantitative Inorganic Analysis; IVth Ed. ELBS, London (1978) K. M. Salaam, K. H. Halawani and S. A. Fakiha, Thermochim. Acta; 204 (1992) 311 P. Sharrock, T. Theophanides and F.Brine, Canad. J. Chem; 51 (1979) 2963 W. Brzyska and B. Galkowska, Polish J. Chem; 72 (1998) 498 G.B. Deacon and R. Philips, Coord. Chem. Rev; 88 (1980) 227 L. P. Battaglia, A. B. Corradi, G. Marcotrigiano. L. Menabue and G.C Pellacani, J. Am. Chem. Soc; 102 (1980) 2663 L. Antolini, L. P. Battaglia, A. B. Corradi, G. Marcotrigiano, L. Menabue, G. C. Pellacani and M. Saladini, Inorg. Chem; 21 (1982) 1391 K. Nakamoto, Infrared & Raman Spectroscopy of Inorganic and Coordination compounds. Wiley, New York, (1978) A. Braibanti, F. Dallavalle, M. A. Pellinghelli and E. Leporati, Inorg. Chem; 7 (1968) 1430 H. Irving and R. J. P. Williams, Nature; 162 (1948) 746 R. S. Drago, Physical Methods in Chemistry Saunders, Philadelphia (1969) A. B. P. Lever Inorganic Electronic Spectroscopy. 2nd Ed, Elsevier, Amsterdam, (1984) K. K. M. Yusuff and R. Sreekala, Thermochim. Acta; 159 (1990) 357 R. H. Holm and M. J. O Connor, Prog. Inorg. Chem; 14 (1971) 241 F. A Cotton and J.J. Wise, Inorg. Chem; 6 (1967) 917 G. Marcotrigiano, L. Menabue, G. C. Pellacani and M. Saladini, Inorg. Chim. Acta; 34 (1979) 43 T. P. Lockhart and D. A. Haitko, Polyhedron; 4 (1985) 1745

43. 44. 45. 46. 47. 48. 49. 50. 51. 52.

146

Chapter 3

53. 54. 55. 56. 57. 58. 59.

P. Zanello, S. Tamburini and P. A. Vigato, Coord. Chem. Rev; 77 (1987) 165 Y. Zhou, Y. Ge and J. Liu, Trans. Met. Chem; 22 (1997) 212 N. H. Pilkington and R. Robson, Austr. J. Chem; 23 (1970) 2225 H. Ham, S. Lee, Y. Kim and M. J. Jun, Bull. Korean. Chem. Soc; 17 (1996) 428 E. Chinea, S. Dominguez, A. Mederos, M.C. Munoz and F. Lioret, Polyhedron; 19 (2000) 1175 J. A. Dean Langes Hand Book of Chemistry 13th Ed, Mcgrew Hill Book 43. Company, New York (1972) 5.18-5.60 K. Nakamoto Infrared & Raman Spectroscopy of Inorganic and coordination compounds. 4th Ed, John Wiley & Son, New York, (1986) Silverstein, Bassler and Morril, Spectroscopic Identification of Organic Compounds, 5th Ed; John Wiley and Sons, Inc E. V. Brown and G. R. Granneman. J.Am. Chem. Soc; 97 (1976) 621 S. P. Sinha, Spectrochim. Acta; 20 (1964) 879 M. V. Garad, Polyhedron; 4 (1985) 1353 K. J. Wynne and P. S. Pearson, Inorg. Chem; 10 (1971) 2735 P. N. Srivastava, R. C. Srivastava and V. K. Srivastava; J. Indian. Chem. Soc; 60 (1983) 891 R. J. H. Clark and C. J. William, Inorg. Chem; 4 (1965) 350 B. Konig Structure and Bonding Springer-Verley, Berlin., Vol.9, (1979) M. Z. Frazer, D. Canningham and J. D. Donaldson, J. Chem, Soc. A; 249 (1971) M. Shakir, P. S. Hameed and F. Firduas, Synth. React. Inorg. Met-Org. Chem; 24 (1994) 1647

60. 61. 62. 63. 64. 65. 66. 67. 68. 69.

Interaction of Lewis-bases with Polymeric Metal(II) Succinates

147

70. 71. 72. 73. 74. 75. 76. 77. 78. 79. 80. 81. 82. 83.

A. B. P. Lever, Inorganic Electronic Spectroscopy, Elsevier, Amsterdam, (1968) 534 N. Saravanan, K. K M. Yusuff, P. V. Suresh and G. N. Prabhu. Synth : React. Inorg. Met-Org. Chem; 26(5) (1996) 901 V. B. Rana, D. P. Singh, P. Singh and M. P. Teotia, Trans. Met. Chem; 36 (1981) 6 T. N. Srivastava, M. A. Siddiqui and S. K. Srivastava, Indian J. Chem; 27 (1988) 550 T. N. Srivastava and P. Kumar. Indian J. Chem; 22 (1983) 878 Y. Nishida and S. Kida, Coord. Chem. Rev; 15 (1975) 279 M. A. Hitchman and T. D. Waite, Inorg. Chem; 15 (1976) 2150 S. N. Shetti, A. S. R. Murty and G. L. Tembe, Indian J. Chem; 32A (1993) 318 M. R. G. Nair and C. P. Prabhakaran, J. Inorg. Nucl. Chem; 43 (1981) 3390 A. H. Maki and R. B. M. Garvey, J. Chem. Phy; 29 (1958) 31 and 35 R. Neiman and D. Kivelson, J. Chem. Phy; 35 (1961) 149 J. Peisach and W. E. Blumberg, Arch. Biochem. Biophy; 165 (1974) 691 B. Singh, B. P. Yadava and R. C. Aggarwal, Indian J. Chem; 23 A (1984) 441 G. M. Sheldrick, SHELXL-97, Program for the refinement of crystal structure, University of Gottingen, Germany, (1997)

Chapter 4 Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II) and their Lewis-base Adducts

4.1

A
base their

Introduction
look at the bonding features in metal succinate complexes with MO6 chromophore (for Ni(II)) and MO4 chromophore (for Co(II) and Cu(II)) and their Lewisof the type MN4O2, MN2O4, MNO5 and MN4 through Lewis-

derivatives

shows that the additional M-N bonds formed

bases are different from the original M-O bonds originating from metal-succinate interaction. While the succinate ligand with chelating nature in anionic form does the charge compensation of the cationic metal, the Lewis-bases simply provide additional M-N coordinate bonds. It can be expected that the metal has more bonding participation with the succinate ligands than with the Lewis-bases in most of the adducts if succinate moieties still remain chelatively binding. We could infer from the preparative stage itself that the Lewis-bases are rather weakly bonded to the metal than to the succinate moiety. It also could be observed in the drying stages that some of the adducts release the Lewis-bases on activating them thermally, resulting in parent complexes. All the spectral data of the adducts also indicate that there is a major electronic modulation in metal carboxylate bonding which is being induced by Lewisbase coordination. These are manifested in the IR spectra (as a change in ), electronic spectra (in parameters like Dq, , B, besides the change in the electronic transitions) and in EPR spectra (the changes in various spin-Hamiltonian parameters). As the Lewis-bases belong to either -donor category (en, pn) or -donor and partially *-acceptor category (py, bipy, phen), it can be expected that the coordinated bases can tune the metal

148

Chapter 4

carboxylate bonding by both their relative donor and acceptor strengths. Significant enough would be the synergetic effect that may originate from the bonded carboxylate group onto the M-N bond formed by metal and Lewis-bases. This is expected to bring about substantial modulation in M-N bond strength and overall stability of the Lewis-base adducts. Further, some of the coordinatively saturated mixed-ligand complexes of metalcarboxylates have been demonstrated to be useful candidates for selective catalytic processes. Since the ligand substitution or substrate interaction can be expected to be operating through a dissociative mechanism in such saturated adducts, it is pertinent to assess the relative bond strengths of the coordinated species in these metal complexes. In this context it occurred to us to look at in some detail the thermal dissociation/decomposition of various Lewis-base adducts developed in our study. Before we discuss the thermal decomposition features of these adducts in detail, it is instructive to look at various reports available in the literature on the thermal behaviour of metal succinate and their adducts. A few reports are available on Cd(II), Ni(II), Co(II) and Cu(II) succinates.(1-4) Brzyska et al(5) reported that Cd(II), Co(II) and Ni(II) succinates with compositions [Cd(suc)].2H2O, [Co(suc)].3H2O and [Ni(suc)].3H2O decompose in two steps to yield the final product as either metal or metal oxides. However, no thermodynamic parameters have been evaluated for them. Thermal features and electrical conductivity measurements of Cu(II) and Zn(II) succinates are also been reported by Nikumbh et al(6). Suzuki et al(7) have reported that manganese(II) succinate decompose differently in CO2 and air. Some reports about Fe(suc).4H2O(8) is also available which shows that the final product

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

149

formed is -Fe2O3. Ceipidor et al(9) reported the decomposition features of K3[Cr(suc)3].3H2O, which involve a three stage decomposition process, the final product being K3CrO3. The thermal behaviour of mixed ligand metal succinates involving Lewis-bases are rather sparse. The study of Masson et al(10) on a few imidazole ligated copper succinate with composition, [Cu(suc)(L)2].2H2O (L = imidazole, 1-methyl imidazole, 2-methyl imidazole, 4-methyl imidazole and 1,2-dimethyl imidazole) shows that the reaction behaviour of 1,2-dimethyl imidazole adduct is different from that of other imidazole derivatives. While imidazole adducts of copper succinate show a three-stage decomposition, thermal the cobalt A adduct of with the composition, reports [Co(suc)(L)2(H2O)].1.5H2O(11), (L = en, phen), exhibits a four stage decomposition. review literature indicates that no systematic thermal dissociation study have been made on Lewis-base adducts of metal succinates. Further, the studies on metal succinates are only minimal without any reference to thermodynamic features associated with them. The composition of various metal succinates developed in our study are seen to be reported earlier in terms of water content. A preliminary study on the parent metal succinates synthesized by us shows that the decomposition features vary from those reported earlier. So it occurred very relevant to us to carry out the thermal behaviour of the metal succinates and their various Lewis-base adducts in a systematic manner, focusing more on the nature of dissociation of the coordinated Lewis-bases and the thermodynamic features associated with each thermal steps.

150

Chapter 4

The thermal analyses were carried out using Seiko Thermal Analyser in an atmosphere of dry N2 with a heating rate of 100C/min. The thermal characterisation of almost all the complexes developed were studied and their thermodynamic and kinetic parameters calculated using a locally developed computer program. The general theories involved in the phenomenological, kinetic and thermodynamic aspects are discussed in Chapter 2.

4.2

Results and Discussion

The thermal decomposition characteristics of the ligand

succinic acid (H2suc) as such, the divalent transition metal succinates (Ni(II), Co(II) and Cu(II)) and their various Lewis-base adducts are studied in N2 atmosphere. For better comparison of the results the instrument settings and the heating rate employed were the same for all the samples. Wendlandt and co-workers studied the relationship

between the thermal stability of metal chelates and the structure of chelating ligands.(12,13) used to study the Usually non-isothermal methods are and mechanisms of thermal In the present investigation, kinetics

decomposition of compounds.(13)

non-isothermal analysis is used as the tool for the investigation of thermal stability of complexes and also for the evaluation of the kinetic parameters of thermal decomposition reactions. The phenomenological and kinetic aspects of the decomposition observed for the samples and the trends in thermal behaviour of various adducts of metal succinates are summarised below.

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

151

4.2.1
4.2.1.1

Phenomenological Aspects
Succinic Acid (HOOCCH2CH2COOH)

The thermal decomposition of the ligand, succinic acid was studied in N2 atmosphere(3) in the temperature range 190-580 0C. The residual percentage was seen to be zero indicating that the ligand was getting completely converted into various gaseous products, The TG and DTA curve for the succinic acid (Fig 4.1) show that it is thermally stable up to 1900C. Its pyrolytic decomposition starts at 1900C (Ti) and finishes at 5800C (Tf) with the total elimination of the sample. No residue is found to be remaining after 5800C indicating that the ligand gets completely decomposed to various gaseous products. The DTA curve of succinic acid (Fig 4.1) shows an endothermic peak at 1850C corresponding to fusion. The value of the fusion enthalpy is seen to be 83 kJ/mol. Liquid succinic acid is seen decomposing immediately with an endothermic peak at 4100C.

Fig 4.1. Thermogram (TG/DTA) of succinic acid in N2

4.2.1.2

Thermal decomposition of nickel(II) succinate in N2

Thermogram of nickel(II) succinate in nitrogen atmosphere given in Fig 4.2 shows a two stage thermal decomposition.(3-5) The initial decomposition starts at 850C (Ti) and progress till 1390C (Tf).

152

Chapter 4

The weight loss corresponding to this stage amounts to 28.97% which is in agreement with the theoretical value of 29.19% for the loss of four molecules of (both coordinated and lattice) water. In the second stage of decomposition (355-3900C) the weight loss of 40.64% could be attributed to the decomposition of [Ni(suc)]n to yield NiO. The residual mass of 30.39% observed in the thermogram is in close agreement with the theoretical value of 30.27% for NiO. The authenticity of the final product NiO was also confirmed by chemical analysis. Some of the thermal features are summarised in Table 4.1.

Fig 4.2. Thermogram (TG/DTG) of [(Ni(H2O)2(suc)).2H2O]n in N2

The decomposition features could be summarised as below.

[(Ni(H2O)2(suc)). 2 H2O] , N2 n 85-139 0C [Ni(suc)] + 4H2O (4.1) n

[Ni(suc)] n

,N2 355 - 390 C

0

gaseous pr odu cts

..(4.2)

Table 4.1 Thermal characteristics of [(Ni(H2O)2(suc)).2H2O]n (1)

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

153

Compound

Temp range (0C) 85-139

Peak temp (0C) 125 382 -

Stages I II -

Wt.loss (in %) Found 28.97 40.64 30.39 (residue) Calcd 29.19 40.54 30.27 (residue)

Probable reaction eq 4.1 eq 4.2 NiO

(1)

355-390 Above 390

4.2.1.3 Lewis-base adducts of nickel(II) succinate The thermal decomposition characteristics of the monomeric as well as the polymeric Lewis-base adducts of nickel(II) succinate are studied only in nitrogen atmosphere. various adducts are summarised below. (a) [Ni(en)2(H2O)2]suc.2H2O, 4 The thermogram of 4 (Fig 4.3) shows that this compound is thermally stable up to 600C, indicated by a well-defined horizontal plateau. The first stage decomposition is seen starting at 600C (Ti) and progressing till 1250C (Tf) with a peak temp of 1110C. The weight loss during this stage amounts to 10.20% indicating the loss of two moles of lattice water (expected value: 9.82%). The second stage of decomposition starts immediately after the first at 1250C (Ti) and ends at 2350C (Tf). During this stage the loss of 1 mole en and two moles of coordinated water take place. The mass loss calculated (26.18%) agrees well with the observed value (26.10%). The third stage initiates at 2350C and ends at 3500C with the loss of remaining 1 mole of en yielding back the 4-coordinate [Ni(suc)]n. The weight loss calculated for this stage (16.36%) agrees well with the observed value (16.05%). The cumulative mass loss from the T.G curve due to stage I, II and III The rate of heating was 100C/min. The phenomenological aspects of the decompositions of

154

Chapter 4

was found to be 52.35% and the residual percentage after the three stages was 47.65% agreeing well with the theoretical percentage of 47.64%. In the fourth stage of decomposition (350-4300C) the weight loss amounting to 31.70% could be attributed to the decomposition of [Ni(suc)]n to yield Ni as the final product. The residual percentage of 15.95% after the complete decomposition is in good agreement with the theoretical value of 16.01%. These data are tabulated in Table 4.2.

Fig. 4.3 Thermogram (TG/DTG) of [Ni(en)2(H2O)]2 suc.2H2O in N2

The decomposition features could be summarised as given below.

, N2 [Ni(en)2(H2O)2] suc.2H2O 60 - 125oC

[Ni(en)2(H2O)2] suc +2H2O (4.3)

[Ni(en)2(H2O)2]suc

, N2 125-235 0C

[Ni(en) suc] n + 2H2O + en . (4.4)

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

155

[Ni (en)suc] n

, N2 235- 350 C
, N2
0

[Ni (suc)] n + en

.(4.5)

[N i (suc)] n

350- 430 C

N i + gaseous products

.(4.6)

Table 4.2. Thermal characteristics of [Ni(en)2(H2O)2]suc.2H2O

Compound Temp range (0C) Peak temp (0C) Wt.loss (in %) Stages Found Calcd Probable reaction

60-125 125-235 [Ni(en)2(H2O)2]suc.2H2O 235-350 350-430 Above 430

111.36 234.22 339.30 410.64 -

I II III IV -

10.20 26.10 16.05 31.70 15.95 (residue)

9.82 26.18 16.36 31.63 16.01 (residue)

eq 4.3 eq 4.4 eq 4.5 eq 4.6 Ni

(b)

[Ni(bipy)2(H2O)2]suc. 2H2O, 5 The thermogram of [Ni(bipy)2(H2O)2]suc.2H2O is shown in

Fig 4.4. The compound is seen decomposing in four stages starting at 500C (Ti) and ending at 3950C. The mass loss in the first decomposition in the range 50-950C with a peak temp 690C (Ts) was found to be 6.80% indicating the loss of two moles of lattice water. The second stage is seen commencing immediately after the first at 950C (Ti) and ending at 1200C (Tf). During this second stage the loss of two moles of coordinated water takes place. The mass loss calculated (6.44%) almost agrees well with the observed value of 7.05 %. The third stage of decomposition initiates at 2400C (Ti) and

156

Chapter 4

ends at 3000C (Tf). The loss in mass corresponding to this decomposition is found to be 27.61%. This could be attributed to the loss of 1 mole of bipy from the adduct. The theoretical value of 27.94% supports this thermal change. The fourth stage of decomposition commences at 3000C (Ti) and progresses till 3950C (Tf). In this stage, the loss of 1mole of bipy together with the decomposition of succinate moiety can be expected to take place to yield NiO as the final product. The mass loss corresponding to this decomposition is 45.98% with the mass of the residue being 12.56% (Table 4.3). Above 3950C, the residue was seen to be stable in the N2 atmosphere.

Fig 4.4. Thermogram (TG/DTG) of [Ni (bipy)2(H2O)2]suc. 2H2O in N2

The decomposition stages could be summarised as shown below.

[Ni(bipy)2(H2O)2]suc. 2H2O

, N2 50- 95 0 C

[Ni(bipy)2(H2O)2]suc. + 2H2O .(4.7)

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

157

[Ni(bipy)2(H2O)2]suc.

, N2 95-120 0 C

[Ni(bipy)2]suc. + 2 H2O ..(4.8)

, N2 [Ni(bipy)(suc)] n + bipy [Ni(bipy)2]suc. 0 240 - 300 C

,N2 NiO + bipy + gaseous produc 300- 3950 C

..(4.9)

[Ni(bipy)(suc)]n

.. (4.10)

Table 4.3. Thermal characteristics of [Ni(bipy)2(H2O)2] suc.2H2O

Temp range (0C) 50-95 95-120 [Ni(bipy)2(H2O)2]suc.2H2O 240-300 300-395 Above 395 Peak temp (0C) 69 117 281 393 Wt.loss (in %) Stages Found I II III IV 6.80 7.05 27.61 45.98 12.56 (residue) Calcd 6.44 6.44 27.94 45.82 13.36 (residue) Probable reaction eq 4.7 eq 4.8 eq 4.9 eq 4.10 NiO

Compound

(c)

[Ni(phen)2(H2O)2]suc.2H2O, 6 The thermogram of [Ni(phen)2(H2O)2]suc.2H2O is shown in

Fig 4.5. It shows an initial mass loss starting at 500C (Ti) and progressing till 950C (Tf). The observed weight loss (6.12%) agrees with the calculated value of 5.6% for the loss of two moles of lattice water. The second stage is seen starting at 1500C, indicating relative stability of the complex formed after the first stage of decomposition. In this stage the loss of two moles of coordinated water takes place. The mass loss calculated (5.60%) agrees with the observed value of

158

Chapter 4

6.08%. The third stage commences at 3000C and ends at 3600C with a mass loss of about 30.98%. This could be attributed to the loss of a mole of phen moiety from the adduct. The theoretical value of 30.82% supports this thermal change. During the fourth stage (360-7050C), the loss of the remaining phen moiety together with the decomposition of suc moiety can be expected to take place to yield NiO as the final product. The mass loss calculated (46.37%) is in agreement with the observed value of 45.62%. The residual mass (11.20%) is in perfect match with the theoretical value of 11.61%. The data are given in Table 4.4.

Fig 4.5. Thermogram (TG/DTG) of [Ni(phen)2(H2O)2]suc.2H2O in N2

The decomposition features are summarised below

[Ni(phen)2 (H2O)2 ]suc. 2 H 2 O ,N 2 50- 95 0 C [Ni(phen)2 (H2 O)2]suc + 2 H2 O

..(4.11)

[Ni(phen)2(H2O)2]suc

,N 2 150 - 205 C
0

[Ni(phen)2]suc + 2 H2O

(4.12)

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

159

[Ni(phen)2]suc

,N2 0 300- 360 C

,N 2

[Ni(phen) suc] n + phen

(4.13)

[Ni(phen)suc] n

360- 705 C

NiO + phen + gaseous products

..(4.14)

Table 4.4 Thermal characteristics of [Ni(phen)2(H2O)2]suc.2H2O

Temp range (0C) 50-95 150-205 [Ni(phen)2(H2O)2] suc.2H2O 300-360 360-705 Above 705 Peak temp (0C) 80 198 353 574 I II III IV Wt. loss (in %) Stages Found 6.12 6.08 30.98 45.62 11.20 (residue) Calcd 5.60 5.60 30.82 46.37 11.61 (residue) Probable reaction eq 4.11 eq 4.12 eq 4.13 eq 4.14 NiO

Compound

(d)

[Ni(H2O)(py)suc]n, 7 From the thermogram given in Fig 4.6, it was observed that

this compound is thermally stable up to 1000C, indicated by a well defined horizontal plateau. The first stage decomposition (100-3550C) starts with the elimination of one mole of pyridine along with the loss of one mole of coordinated water yielding back the 4-coordinated [Ni(suc)]n. The mass loss calculated (35.73%) during this stage agrees well with the observed value of 36.20%. In the second stage of decomposition (355-4200C) the weight loss amounting to 37.04% could be attributed to the decomposition of [Ni(suc)]n to yield NiO as the final product. The residual percentage of 26.76% after the complete decomposition is in good agreement with the theoretical value of 27.48%. These data are tabulated in Table 4.5.

160

Chapter 4

Fig 4.6. Thermogram (TG/DTG) of [Ni(H2O)(py)suc]n in N2

The decomposition pattern could be summarized as given below

[Ni(H2O)(py)suc]n

, N2 100-355 0 C

[Ni(suc)] n + py

H2O

.(4.15)

, N2 NiO + gaseous products [Ni(suc)]n 355-420 0 C

(4.16)

Table 4.5. Thermal characteristics of [Ni(H2O)(py)suc]n

Compound Temp range (0C) 100-355 [Ni(H2O)(py)suc]n 355-420 Above 420 Peak temp (0C) 170 410 Stages I II Wt.loss (in %) Found 36.20 37.04 26.76 (residue) Calcd 35.73 36.79 27.48 (residue) Probable reaction eq 4.15 eq 4.16 NiO

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

161

(e)

[Ni(pn)2(suc)]n, 8 The thermogram of [Ni(pn)2(suc)]n is shown in Fig 4.7. This

compound is seen to be stable up to 2300C indicated by a well defined horizontal plateau in the TG curve. In the first and second stages, (230-2700C) and (270-3500C), the loss of each molecule of pn takes place leaving back the 4-coordinate, [Ni(suc)]n compound. The cumulative mass loss in both the stages was found to be 46.10% (27.90% + 18.20%), which is in good agreement with the theoretical value of 45.90%. In the third stage of decomposition (350-4200C), the weight loss amounting to 35.60% could be attributed to the decomposition of [Ni(suc)]n to Ni and gaseous products. Above 4200C, the residual compound was seen to be stable in the nitrogen atmosphere. The data are given in Table 4.6.

Fig 4.7. Thermogram (TG/DTG) of [Ni(pn)2suc]n in N2

162

Chapter 4

The decomposition features could be summarized as given below

[Ni(pn)2(suc)]n

, N2 230-270 0C

[Ni(suc)(pn)] n

pn ................... (4.17)

[Ni(suc)(pn)]n

, N2 270-3500 C
, N2

[Ni(suc)]n + pn ...................... (4.18)

[Ni(suc)]n

350 - 4200 C

Ni+ gasesous products

.................. (4.19)

Table 4.6 Thermal characteristics of [Ni(pn)2suc]n

Compound Temp range (0C) 230-270 270-350 [Ni(pn)2suc]n 350-420 Above 420 Peak temp (0C) 276 336 412 Stages I II III Wt. loss (in %) Found 27.90 18.20 35.60 18.30 (residue) Calcd 22.95 22.95 35.93 18.17 (residue) Probable reaction eq 4.17 eq 4.18 eq 4.19 Ni

4.2.1.4 Thermal decomposition of cobalt(II) succinate in nitrogen The thermogram of [(Co(suc)).2H2O]n in nitrogen atmosphere given in Fig 4.8 shows a two stage thermal decomposition.(3-5) It shows an initial mass loss which is starting at 600C (Ti) and ending at 1300C (Tf). During this stage the mass loss was found to be 17.38% indicating the loss of two moles of lattice water. The second stage of decomposition starts at 3700C (Ti) and progresses till 6100C, with a mass loss amounting to 54.33%. A stable base line after the second decomposition shows the completion of the

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

163

reaction with a residual percentage of 28.29%. The decomposition features are given in Table 4.7.

Fig 4.8. Thermogram (TG/DTG) of [(Co(suc)).2H2O]n in N2

The observed decomposition features are given below

[(Co(suc)). 2H2 O] n

,N2 0 60- 130 C

[Co(suc)] n + 2H 2 O ............... (4.20)

[Co(suc)] n

,N 2 370 - 610 C
0

Co + gaseous products

................... (4.21)

Table 4.7 Thermal characteristics of [(Co(suc)).2H2O]n (2)

Compound Temp range (0C) 60-130 (2) 370-610 Above 610 Peak temp (0C) 103 438 Stages I II III Wt.loss (in %) Found 17.38 54.33 28.29 (residue) Calcd 17.07 54.99 27.94 (residue) Probable reaction eq 4.20 eq 4.21 Co

164

Chapter 4

4.2.1.5 (a)

Lewis-base adducts of cobalt(II) succinate

[(Co(en)2(suc)).H2O]n, 9 The thermogram of [(Co(en)2(suc).H2O]n is shown in Fig 4.9.

It shows an initial decomposition which is starting at 550C (Ti) and going upto 1050C (Tf), with a mass loss of 6.10% indicating the loss of one mole of lattice water (expected : 5.75%). The second stage was seen starting at 2200C (Ti) and ending at 3600C. In this stage the loss of two moles of en takes place. The loss in mass calculated (38.35%) agrees well with the observed value of 38.20%. The third stage stars immediately after the second with the weight loss amounting to 37.30% could be attributed to the decomposition of [Co(suc)]n to Co and gaseous products. The residual percentage of 18.40% after the complete decomposition is in good agreement with the theoretical value of 18.53%. The details of thermal decomposition features are shown in Table 4.8.

Fig. 4.9. Thermogram (TG/DTG) of [(Co(en)2(suc)).H2O]n in N2

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

165

[(Co(en)2(suc)).H2O] n

, N2 55 - 105 C
0

[Co(en) (suc)] + H2O ....... (4.22) 2 n

[Co(en)2 (suc)]

, N2 n 220 - 360 0C , N2

[Co(suc)] n

2en ...................... (4.23)

[Co(suc)]

360-585 0C

Co + gasesous products

................... (4.24)

Table 4.8. Thermal characteristics of [(Co(en)2suc).H2O]n

Compound Temp range (0C) 55-105 220-360 [(Co(en)2suc).H2O]n 360-585 Above 585 Peak temp (0C) 98 270 385 Stages I II III Wt.loss (in %) Found 6.10 38.20 37.30 18.40 (residue) Calcd 5.75 38.35 37.01 18.53 (residue) Probable reaction eq 4.22 eq 4.23 eq 4.24 Co

(b)

[Co(bipy)2(H2O)2]suc.2H2O, 10 The thermogram of the adduct is shown in Fig 4.10. It shows

an initial decomposition starting at 400C (Ti) and ending at 1800C (Tf) with a peak temp (Ts) of 1250C. The weight loss corresponding to this decomposition amounts to 13.01% (expected : 12.87%). In this stage the loss of 2 moles of each coordinated and lattice water takes place. The second stage of decomposition starts in the range 180-2800C. During this stage the loss of a mole of bipy takes place. The mass loss calculated (27.93%) almost agrees with the observed value (28.10%). The third stage of decomposition is seen initiating at 2800C and ending at 3600C (Tf) with a Ts of 3200C. The loss in mass corresponding to this decomposition stage (27.60%) could be

166

Chapter 4

attributed to the loss of the remaining bipy from the adduct leaving back the parent complex. The theoretical value of 27.93% supports this thermal change. In the fourth stage of decomposition (360-5300C) the weight loss amounting to 20.59% could be attributed to the decomposition of [Co(suc)]n to Co and gaseous products. The residual percentage of 10.70% after the complete decomposition is in good agreement with the theoretical value of 10.54%. The details of thermal decomposition features are summarized in Table 4.9.

Fig 4.10. Thermogram (TG/DTG) of [Co(bipy)2(H2O)2]suc.2H2O in N2

[Co(bipy)2(H2O)2]suc.2 H2O
)

, N2 40-180 0C

[Co(bipy) ]suc + 4H 2O .(4.25 2

[Co(bipy)2]suc

, N2 180-280 0C

[Co(bipy)suc] n + bipy ................ (4.26)

[Co(suc)] n + bipy ....................... (4.27)

, N2 [Co(bipy)suc]n 280-360 0 C

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

167

[Co(suc)] n

, N2 360-530 0 C

Co + gaseous products

.................... (4.28)

Table 4.9 Thermal characteristics of [Co(bipy)2(H2O)2]suc.2H2O

Compound Temp range (0C) 40-180 180-280 [Co(bipy)2(H2O)2]suc.2H2O 280-360 360-530 Above 530 Peak temp (0C) 125 185 320 445 Stages I II III IV Wt.loss (in %) Found 13.01 28.10 27.60 20.59 10.70 (residue) Calcd. 12.87 27.93 27.93 20.73 10.54 (residue) Probable reaction eq 4.25 eq 4.26 eq 4.27 eq. 4.28 Co

(c)

[Co(phen)2]suc.2H2O, 11 Fig 4.11 gives the thermogram of the adduct. The initial

decomposition was found to be in the range 50-800C with a peak temp of 620C. But the second and third stages of decomposition were found to be in the range 270-3350C and 335-7550C respectively. The maximum mass loss was taking place at a temp (Ts) of 3300C in the second stage and at 5600C in the third stage. Above 7550C, the residue was seen to be stable in nitrogen atmosphere. The data are tabulated in Table 4.10. In the first step the loss of two molecules of lattice water takes place. The weight loss corresponding to this stage is observed to be 6.10% which is in close agreement with the calculated value of 5.93%. During the second stage 1 mole of phen moiety escapes from the complex. The weight loss corresponding to this stage is seen to be 31.98% which is in close agreement with the calculated value of 32.64%. In the third stage the loss of the

168

Chapter 4

remaining

phen

moiety

together with the decomposition of

succinate moiety can be expected to take place to yield CuO as the final product. The mass loss corresponding to this stage is observed to be 49.47% which is in good agreement with the calculated value of 49.09%. The residual mass of 12.45% (expected for CoO) observed in the thermogram agrees well with the theoretical value of 12.34%.

Fig 4.11. Thermogram (TG/DTG) of [Co(phen)2]suc 2H2O in N2

The thermal decomposition features are given below.

[Co(phen)2]suc.2H 2 O

, N2 50-80 0C

[Co(phen)2]suc + 2H 2 O .. (4.29)

[Co(phen)2]suc

, N2 270 -335 C
, N2
0

[Co(phen)(suc)] n + phen .............. (4.30)

[Co(phen)(suc)]

335 -755 C

CoO + phen + gaseous products

(4.31)

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

169

Table 4.10 Thermal characteristics of [Co(phen)2]suc.2H2O

Compound Temp. range (0C) 50-80 [Co(phen)2] suc. 2H2O 270-335 335-755 Above 755 Peak temp (0C) 62 330 560 Stages I II III Weight loss % Found 6.10 31.98 49.47 12.45 (residue) Calcd 5.93 32.64 49.09 12.34 (residue) Probable reaction eq. 4.29 eq. 4.30 eq. 4.31 CoO

(d)

[Co(py)2(suc)]n, 12 The theromogram of [Co(py)2(suc)]n is shown in Fig. 4.12

Fig. 4.12. Thermogram (TG/DTG) of [Co(py)2(suc)]n in N2

It shows an initial decomposition which is starting at 980C (Ti) and going upto 1450C (Tf). The weight loss corresponding to this decomposition stage amounts to 23.42%. In this stage a mole of pyridine moiety escapes from the adduct. The second stage of decomposition seen initiating immediately at 1450C and ending at 3650C with a loss in mass of 23.42%. This shows that again the loss of 1 mole pyridine moiety from the adduct. The total weight

170

Chapter 4

loss after the two decomposition stages (46.84%) is in agreement with the theoretical value of 47.48% for the loss of two pyridine moieties. In the third stage of decomposition (365-4250C), the weight loss (29.80%) could be attributed to the decomposition of [Co(suc)]n to yield CoO and gaseous products. The residual mass of 23.36% (for CoO) observed in the thermogram agrees well with the theoretical value of 22.49%. The details of thermal decomposition features are shown in Table 4.11. Table 4.11. Thermal characteristics of [Co(py)2(suc)]n
Compound Temp. range (0C) 98-145 145-365 [Co(py)2suc]n 365-425 Above 425 Peak temp (0C) 139 281 382 Stages I II III Weight loss % Found 23.42 23.42 29.80 23.36 (residue) Calcd 23.74 23.74 30.03 22.49 (residue) Probable reaction eq. 4.32 eq. 4.33 eq. 4.34 CoO

The thermal decomposition features are given below

[Co(py)2(suc)] n

, N2 98 - 145 0 C
, N2 145 - 365 0C , N2

[Co(py)(suc)] n + py

................ (4.32)

[Co(py)(suc)] n

[Co(suc)] n + py

.................... (4.33)

[Co(suc)] n

CoO + gaseous products

365 - 425 C
4.2.1.6 Thermal decomposition of copper(II) succinate in nitrogen The thermogram of copper(II) succinate is shown in Fig 4.13. This compound is seen to be thermally stable upto 3000C indicated by a well defined horizontal plateau in its TG curve and has only one

............... (4.34)

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

171

thermal step. The weight loss is seen starting at 3000C (Ti) and progressing till 3550C (Tf) with a peak temperature of 3520C (Ts). The loss in mass corresponding to this step amounts to 56.10% which is in good agreement with the calculated value of 55.70% for the decomposition of suc moiety to yield the final product as CuO. The residual mass of 43.90% (expected for CuO) is in good agreement with the calculated value of 44.30%. The decomposition features are given in Table 4.12.

Fig 4.13. Thermogram (TG/DTG) of [Cu(suc)]n in N2

The observed decomposition feature is given below.

[Cu(suc)] n

, N2 300 -355 C
0

CuO + gaseous products

.................... (4.35)

172

Chapter 4

Table 4.12. Thermal characteristics of [Cu(suc)]n (3)

Compound Temp range (0C) 300-355 (3) Above 355 Peak temp (0C) 352 Stages I Wt.loss (in %) Found 56.10 43.90 (residue) Calcd 55.70 44.30 (residue) Probable reaction eq 4.35 CuO

4.2.1.7 (a)

Lewis-base adducts of copper(II) succinate

[Cu(en)suc]n, 14 From the thermogram given in Fig. 4.14 it was observed that

this compound is seen to be thermally stable upto 2300C, indicated by a well defined horizontal plateau. The initial decomposition starts at 2300C and progresses till 2600C with a peak temperature of 2450C. In this stage the loss of a mole of en from the adduct is seen, leaving back the parent complex. The mass loss calculated (25.04%) was in good agreement with the observed value of 25.70%. The second stage of decomposition is seen initiating at 2600C (Ti) and ending at 5800C (Tf) with a peak temperature of 4800C (Ts). The weight loss calculated in this stage was found to be 41.75% which is in perfect match with the observed value of 42.10%. This could be attributed to the decomposition of [Cu(suc)]n to yield CuO as the final product. The residual mass of 32.20% (for CuO) is in good agreement with the theoretical value of 33.21%. The data are given in Table 4.13.

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

173

Fig 4.14. The Thermogram (TG/DTG) of [Cu(en)suc)n in N2

The decomposition features are given below

[Cu(en)suc] n

, N2 230- 260 C
0

[Cu(suc)] n

en

........................ (4.36)

[Cu(suc)] n

, N2 260-580 C
0

CuO

gaseous products

. (4.37)

Table 4.13 Thermal characteristics of [Cu(en)suc)]n

Compound Temp range (0C) 230-260 [Cu(en)suc)]n 260-580 Above 580 Peak temp (0C) 245 480 Stages I II Wt.loss (in %) Found 25.70 42.10 32.20 (residue) Calcd 25.04 41.75 33.21 (residue) Probable reaction eq 4.36 eq 4.37 CuO

174

Chapter 4

(b)

[Cu(en)2(H2O)2]suc, 15 From the thermogram given in Fig 4.15, it was observed

that this compound is thermally stable upto 1100C, indicated by a well defined horizontal plateau. The first stage decomposition is seen starting at 1100C (Ti) and progressing till 1500C (Tf) with a peak temperature of 1350C (Ts). This agrees well with the loss of two moles of coordinated water from the adduct (expected: 10.73%). During the second stage (150-2600C), the loss of two moles of en takes place yielding back the parent complex. The mass loss calculated (35.76%) agrees well with the observed value of 36.20% for the loss of two moles of en. The third stage starts immediately at 2600C and ends at 5800C with a weight loss amounting to 29.60%. This could be attributed to the decomposition of [Cu(suc)]n to yield CuO as the final product. The residual mass of 23.65% (for CuO) is in good agreement with the theoretical value of 23.71% (Table 4.14).

Fig 4.15. Thermogram (TG/DTG) of [Cu(en)2(H2O)2]suc in N2

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

175

The decomposition features could be summarised as given below.

[Cu(en)2(H2O)2]suc

, N2 110 -150 C
0

[Cu(en)2]suc + 2H2 O ........ (4.38)

............... (4.39)

[Cu(en)2 ] suc

, N2 [Cu(suc)] n + 2 en 150-260 0C
, N2 260 -580 C
0

[Cu(suc)] n

CuO + gaseous products

............... (4.40)

Table 4.14. Thermal characteristics of [Cu(en)2(H2O)2]suc

Temp range (0C) 110-150 150-260 [Cu(en)2(H2O)2]suc 260-580 Above 580 Peak temp (0C) 135 245 520 I II III Wt.loss (in %) Stages Found 10.55 36.20 29.60 23.65 (residue) Calcd 10.73 35.76 29.80 23.71 (residue) Probable reaction eq 4.38 eq 4.39 eq 4.40 CuO

Compound

(c)

[Cu(bipy)(suc)]n, 16 The thermogram of the adduct is given in Fig 4.16. This

compound is seen stable upto 2800C indicated by a well defined horizontal plateau in its TG curve. It shows an initial decomposition which starts at 2800C (Ti) and progresses till 3300C (Tf) with a peak temperature (Ts) of 3230C. The weight loss corresponding to this stage amounts to 63.03% for the escape of a mole of bipy moiety together with the decomposition of succinate moiety can be expected due to the yield of CuCO3 as the final product (expected: 63.20%). In the second stage of decomposition

176

Chapter 4

(330-3900C), the weight loss (13.38%) could be attributed to the decomposition of CuCO3 to yield CuO and CO2. The residual mass of 23.59% (for CuO) observed in the thermogram agrees well with the theoretical value of 23.69%. The decomposition features are summarised in Table 4.15.

Fig 4.16. Thermogram (TG/DTG) of [Cu(bipy)(suc)]n in N2

The observed decomposition features are given below

[Cu(suc)bipy]n

, N2 280 -330 C
0

CuCO3 + bipy + gaseous products

.....(4.41)

CuCO3

, N2 330 -390 0 C

CuO + CO2

.............. (4.42)

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

177

Table 4.15. Thermal characteristics of [Cu(bipy)(suc)]n

Temp range (0C) 280-330 [Cu(bipy)(suc)]n 330-390 Above 390 Peak temp (0C) 323 368 Wt.loss (in %) Stages Found I II 63.03 13.38 23.59 (residue) Calcd 63.20 13.11 23.69 (residue) Probable reaction eq 4.41 eq 4.42 CuO

Compound

(d)

[Cu2(phen)4(suc)]suc.12.5H2O, 17 The thermogram of the adduct is shown in Fig 4.17. The

initial decomposition starts at 400C (Ti) and has Ts at 1020C and Tf at 1700C. The weight loss corresponding to this stage is 16.25% which is in good agreement with the calculated value of 16.34% for the loss of 12.5 moles of H2O from [Cu2(phen)4(suc)]suc.12.5H2O. The second stage initiates at 1700C (Ti), has Ts at 2540C and Tf at 2900C. The mass loss during this stage was found to be 28.90% which is in perfect match with the calculated value of 28.79% for the loss of 2 moles of phen moiety. The third stage commences at 2900C (Ti) and ends at 620 0C with a Ts of 3170C. The mass loss during this stage was found to be 43.20% which is in good agreement with the calculated value of 43.32% for the decomposition of the remaining phen along with suc moiety to yield the final product as CuO. The residual mass of 11.65% (for CuO) agrees with the theoretical value of 11.55%. The decomposition features are summarised in Table 4.16.

178

Chapter 4

Fig 4.17. Thermogram (TG/DTG) of [Cu2(phen)4(suc)]suc.12.5H2O in N2

The decomposition features could be summarised in below.

[Cu2(phen)4(suc)]suc.12.5H2O

, N2 40 - 1700 C

[Cu2(phen)4(suc)]suc + 12.5H2O
.(4.43)

[Cu2(phen)4(suc)]suc

, N2 170 - 290 0C

[Cu2(phen)2(suc)]suc + 2 phen
(4.44)

[Cu2(phen)2(suc)]suc

, N2 gaseous products .(4.45) 2 CuO + 2 phen + 290 - 6200 C

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

179

Table 4.16. Thermal characteristics of [Cu2(phen)4(suc)]suc.12.5H2O

Compound Temp range (0C) 40-170 170-290 [Cu2(phen)4 (suc)]suc.12.5H2O 290-620 Above 620 Peak temp (0C) 102 254 317 Stages I II III Wt.loss (in%) Found 16.25 28.90 43.20 11.65 (residue) Calcd 16.34 28.79 43.32 11.55 (residue) Probable reaction eq 4.43 eq 4.44 eq 4.45 CuO

(e)

[Cu(py)2(suc)]n, 18 The thermogram of [Cu(py)2(suc)]n is shown in Fig 4.18. It was

found that the compound is thermally stable up to 1800C indicated by a horizontal well defined plateau. The thermal decomposition of this compound is seen to be taking place in two stages. The first stage of decomposition is in the range 180-2600C with a peak temp of 2250C. In this stage the loss of a mole of pyridine moiety from the adduct takes place (expected: 23.42%). In the second stage of decomposition (260-3900C), the mass loss was found to be 52.60% which is in perfect match with the calculated value of 53.03%. This could be attributed to the loss of 1 mole of pyridine together with the decomposition of the succinate moiety to yield CuO as the final product. The residual mass of 24.10% (for CuO) observed in the thermogram agrees with the theoretical value of 23.55%. The details of thermal decomposition features are shown in Table 4.17.

180

Chapter 4

Fig 4.18. Thermogram (TG/DTG) of [Cu(py)2(suc)]n in N2

The observed decomposition feature is given below

[Cu(py)2suc] n

, N2 180 260 0C

[Cu(py)suc] n + py .................... (4.46)

[Cu(py)suc] n

, N2 260 - 390 0C

CuO + py + gaseous products

............ (4.47)

Table 4.17 Thermal characteristics of [Cu(py)2(suc)]n

Compound Temp range ( 0C) 180-260 [Cu(py)2(suc)]n 260-390 Above 390 Peak temp ( 0C) 225 349 Stages I II Wt.loss (in %) Found 23.30 52.60 24.10 (residue) Calcd 23.42 53.03 23.55 (residue) Probable reaction eq 4.46 eq 4.47 CuO

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

181

(f)

[Cu(pn)suc]n, 19 The thermogram of the compound is given in Fig 4.19. This

compound is found to be thermally stable upto 2400C indicated by a well defined horizontal plateau. The initial decomposition starts at 2400C and progresses till 2600C with a peak temperature of 2480C. In this stage a mole of pn escapes from the adduct yielding back the parent complex. The mass loss calculated in this stage (29.22%) is in good agreement with the observed value of 28.90%. The second stage of decomposition starts at 2600C (Ti) and ends at 6250C (Tf) with a peak temperature of 5580C (Ts). The mass loss corresponding to this decomposition is 39.70% with the mass of the residue being 31.40%. This stage could be attributed to the decomposition of suc moiety from [Cu(suc)]n to yield CuO as the final product. The data are tabulated in Table 4.18.

Fig 4.19. The thermogram (TG/DTG) of [Cu(pn)suc]n in N2

182

Chapter 4

The decomposition features could be summarized below.

[Cu(pn)suc] n

, N2 240 - 260 C
0

[Cu(suc)] n

pn

................. (4.48)

[Cu(suc)] n

, N2 CuO 260 - 625 0 C

gaseous products

.................. (4.49)

Table 4.18. Thermal characteristics of [Cu(pn)suc]n

Compound Temp range (0C) 240-260 [Cu(pn)suc)]n 260-625 Above 625 Peak temp (0C) 248 558 Stages I II Wt.loss (in %) Found 28.90 39.70 31.40 (residue) Calcd 29.22 39.42 31.36 (residue) Probable reaction eq 4.48 eq 4.49 CuO

(g)

[Cu(pn)2(H2O)2]suc, 20 The thermogram of [Cu(pn)2(H2O)2]suc is shown in Fig 4.20. This

compound is found to be thermally stable upto 1200C indicated by a well defined horizontal plateau. The initial decomposition starts with the elimination of two moles of coordinated water. This stage commences at 1200C and progresses till 2000C with a peak temp of 1400C (Ts). The weight loss during this stage amounts to 9.80% which is in good agreement with the calculated value of 9.90%. The second stage of decomposition starts at 2000C (Ti) and ends at 2500C (Tf) with a mass loss amounts to 41.15% which agrees with the expected value of 40.75% for the loss of two moles of pn from the adduct. The third stage of decomposition is seen initiating at 2500C and ending at 5400C with a peak temperature of 5200C (Ts). The weight loss during this stage The amounts to 26.95%. This could be attributed to the decomposition of suc moiety from [Cu(suc)]n to yield CuO as the final product.

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

183

residual mass of 22.10% (for CuO) is in close agreement with the expected value of 21.86%. The data are given in Table 4.19.

Fig 4.20. The thermogram (TG/DTG) of [Cu(pn)2(H2O)2]suc in N2

Table 4.19 Thermal characteristics of [Cu(pn)2(H2O)2]suc

Compound Temp range (0C) 120-200 200-250 [Cu(pn)2(H2O)2]suc 250-540 Above 540 Peak temp (0C) 140 238 520 Stages I II III Wt.loss (in %) Found 9.80 41.15 26.95 22.10 (residue) Calcd 9.90 40. 75 27.49 21.86 (residue) Probable reaction eq 4.50 eq 4.51 eq 4.52 CuO

The decomposition features are summarised below.

[Cu(pn)2(H2O)2]suc

, N2 120 - 200 C , N2
0 0

[Cu(pn)2]suc

2 H2O .......... (4.50)

................... (4.51)

[Cu(pn)2]suc
[Cu(suc)] n

200 - 250 C
, N2 5400 C

[Cu(suc)] n + 2 pn
+

250 -

CuO

gaseous products .................. (4.52)

184

Chapter 4

4.2.2 Kinetic Aspects

The kinetic parameters for the thermal decomposition stages of the Lewis-base adducts of nickel(II), cobalt(II) and copper(II) succinates evaluated from the slope and intercept of the linear plots (given in Fig 4.21-4.23) are tabulated in Table 4.20-4.22 respectively. Coats-Redfern(14) method is employed for this, being one of the best approaches recommended by several authors.(15-17) The theory involved is discussed in detail in Chapter 2.

-6.0

-7.5 -8.0

Lewis-base adducts of 1

Stage I

Lewis-base adducts of 1
-6.6 -7.2

Stage II

log [g()/T ]

-8.5

b a c d

log [g()/T ]

-7.8 -8.4 -9.0 -9.6

-9.0 -9.5 -10.0

b a e d
1.6 1.8 2.0 2.2 2.4 2.6

e
-10.5 1.8 2.0 2.2 2.4 2.6 2.8 3.0

-10.2

1000 / T

1000 / T

(i)

(ii)

-6.5 -7.0 -7.5

Lews-base adducts of 1

Stage III

-6.5 -7.0 -7.5

Lewis-base adducts of 1

Stage IV

log [g()/T ]

b
-8.0 -8.5 -9.0

log [g()/T ]

-8.0

b
-8.5 -9.0

e
-9.5 1.38 1.44 1.50 1.56 1.62 1.68

a
1.74 1.80

-9.5 1.1 1.2

c
1.3 1.4

a
1.5

1000 / T

1000 / T

(iii)

(iv)

Fig 4.21

log (g()/T2) vs 1000/T plots for the thermal decomposition of Lewis-base adducts of [(Ni(H2O)2suc).2H2O]n, 1; (i) Stage 1; (ii) Stage II; (iii) Stage III; (iv) Stage IV: (a) [Ni(en)2(H2O)2]suc.2H2O, 4 (b) [Ni(bipy)2(H2O)2]suc.2H2O, 5 (c) [Ni(phen)2(H2O)2]suc.2H2O, 6 (d) [Ni(py)(H2O)suc]n,7(e) [Ni(pn)2suc]n, 8

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

185

-7.5

Stage I

-7.0

Lewis-base adducts of 2
-7.5

Stage II

-8.0
-8.0

log [g()/T ]

-8.5

log [g()/T ]

-8.5

-9.0

b c d
2.6 2.8 3.0

-9.0

c
-9.5

-9.5

Lewis-base adducts of 2
2.2 2.4

a
3.2

a
-10.0 1.6 1.7 1.8 1.9 2.0 2.1

d
2.2 2.3

b
2.4

1000 / T

1000 / T

(i)

(ii)

-8.4

Stage III
-8.8

Stage IV
-8.8

-9.2

-9.2

log [g()/T ]

log [g()/T ]

-9.6

-9.6

-10.0

-10.0

-10.4

-10.4

b Lewis-base adducts of 2
1.0 1.1 1.2 1.3

d
1.4

c
1.6

Lewis-base adducts of 2
1.8 2.0

c
1.4 1.5 1.6

1000 / T

1000 / T

(iii) Fig 4.22

(iv)

log (g()/T2) vs 1000/T plots for the thermal decomposition of Lewis-base adducts of [(Co(suc)) 2H2O]n, 2; (i) Stage 1; (ii) Stage II; (iii) Stage III; (iv) Stage IV: (a) [(Co(en)2suc).H2O]n, 9 (b) [Co(bipy)2(H2O)2]suc.2H2O, 10 (c) [Co(phen)2]suc.2H2O, 11 (d) [Co(py)2suc]n, 12

186

Chapter 4

-6.0 -6.6 -7.2

Lewis-base adducts of 3

Stage I

log g (a)/T

-7.8

c
-8.4

d
-9.0 -9.6

a
1.6 1.8 2.0

f
2.2

e
2.4

b
2.6 2.8

g
3.0 3.2

1000 / T

(i)

-6.0

Lewis-base adducts of 3
-6.6 -7.2

Stage II

-8.5

Lewis-base adducts of 3

Stage III

-9.0

log [g()/T ]

-7.8 -8.4 -9.0 -9.6

log [g()/T ]

d b e g

-9.5

-10.0

-10.2

g d

a
1.2 1.5

c
1.8

f
2.1

b
1.6 1.7

1.1

1.2

1.3

1.4

1.5

1000 / T

1000 / T

(ii) Fig 4.23

(iii)

log (g()/T2) vs 1000/T plots for the thermal decomposition of Lewis-base adducts of [Cu(suc)]n, 3; (i) Stage 1; (ii) Stage II; (iii) Stage III: (a) [Cu(en)suc]n, 14 (b) [Cu(en)2(H2O)2]suc , 15 (c) [Cu(bipy)suc]n, 16 (d) [Cu2(phen)4(suc)]suc.12.5 H2O, 17 (e) [Cu(py)2suc]n, 18 (f) [Cu(pn)suc]n, 19(g) [Cu(pn)2(H2O)2]suc, 20

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

187

Table 4.20. Kinetic parameters for the thermal decomposition stages of Lewis-base adducts of nickel(II) succinate
Stage I Compound Ea kJ/mol A s-1 S J/K/mol Ea kJ/mol A s-1 S J/K/mol Ea kJ/mol A s-1 S J/K/ mol Ea kJ/ mol A s-1 S J/K/ mol Stage II Stage III Stage IV

[Ni(en)2(H2O)2]suc.2H2O

79.63

36.28

-217.15

118.84

254.98

-203.28

221.85

296315.30

-146.54

246.54

121644.8

-154.48

[Ni(bipy)2(H2O)2]suc.2H2O

76.45

83.27

-209.29

125.11

1035.68

-151.22

233.90

2.11 10-7

-109.94

316.98

6.01 108

-83.52

[Ni(phen)2(H2O)2]suc.2H2O

70.81

10.16

-227.27

101.31

22.52

-222.92

288.98

1.99 108

-92.24

97.86

6.94 10-2

-276.40

[Ni(py)(H2O)(suc)]n

42.17

2.30 10-2

-279.20

299.20

5127479

-123.33

[Ni(pn)2suc]n

296.82

2.98 109

-69.12

164.22

946.44

-193.87

220.94

23104.7

-168.33

188

Chapter 4

Table 4.21. Kinetic parameters for the thermal decomposition stages of Lewis -base adducts of cobalt(II) succinate
Stage I Stage II Stage III Stage IV

Compound

Ea kJ/mol

A s-1

S J/K/mol

Ea kJ/mol

A s-1

S J/K/mol

Ea kJ/mol

A s-1

S J/K/mol

Ea kJ/mol

A s-1

S J/K/mol

[(Co(en)2suc).H2O]n

69.63

10.73

-227.04

96.67

4.71

-236.97

56.51

109 10-2

-289.03

[Co(bipy)2(H2O)2]suc.2H2O

35.77

3.92 10-2

-274.08

96.43

20.87

-223.09

76.29

0.2325

-262.75

97.03

0.2497

-263.72

[Co(phen)2]suc.2H2O

90.02

692.51

-191.51

182.01

15698.19

-170.44

313.06

4.56 107

-104.88

[Co(py)2suc]n

62.52

0.7984

-249.52

66.35

0.1209

-267.71

257.61

201150.9

-150.02

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

189

Table 4.22.

Kinetic parameters for the thermal decomposition stages of Lewis-base adducts of copper(II) succinate
Stage I Stage II Stage III

Compound Ea kJ/mol A s-1 S J/K/mol Ea kJ/mol A s-1 S J/K/mol Ea kJ/mol A s-1 S J/K/mol

[Cu(en)suc]n

139.38

395.99

-199.77

66.61

8.37 10-3

-292.15

[Cu(en)2(H2O)2]suc

112.90

1002.39

-189.92

59.26

0.1265

-266.51

79.39

204 10-2

-285.36

[Cu(bipy)(suc)]n

154.38

6621.11

-177.52

198.79

4219.96

-181.87

[Cu2(phen)4suc]suc.12.5H2O

44.59

0.1963

-260.34

63.70

0.2187

-163.21

148.36

2.72

-245.04

[Cu(py)2suc]n

107.80

40.36

-218.43

98.63

12.49

-230.03

[Cu(pn)(suc)]n

247.64

6.14 107

-100.20

55.43

6.16 10-3

-294.57

[Cu(pn)2(H2O)2]suc

65.79

0.7565

-249.89

125.90

181.95

-206.12

64.07

9.69 103

-291.63

190

Chapter 4

The activation energies, Ea, in the first stage of thermal decomposition of the various Lewis-base adducts of nickel(II) succinate are in the range 79-296 kJ/mol. The values for the second, third and fourth stages of decomposition are seen in the ranges 101299 kJ/mol, 220-288 kJ/mol, and 97-316 kJ/mol respectively. The corresponding values of entropy of activation (S) for this decompositions fall in the ranges 69 to 279.20, -123 to 222.92, -92 to 168.33 and 83 to 276.40 J/K/mol for the first, second, third and fourth stages of decompositions respectively. The pre-exponential factors vary in a wide ranges of values as 2.30 10-2 to 2.98 to 6.01 108 s-1 in the third stage of decomposition. However, the activation energies in the first and second stages of decomposition of Lewis-base adducts of cobalt(II) succinate are found to be lower than that of nickel(II) succinate analogues, which are in the range 35-90 kJ/mol and 66-182 kJ/mol respectively. For the third stage it was in between 56-313 kJ/mol. The corresponding entropy of activation falls in the range 191 to 274 J/K/mol (stage I), -170 to 267 J/K/mol (stage II) and -104 to 289 J/K/mol (stage III). The pre-exponential factors are also seen varying from 3.92 201150.9 s-1 (stage III). But the activation energies for all the stages of decomposition of Lewis-base adducts of copper(II) succinate are found to be lower than that of nickel(II) succinate analogues, which are in the range 44-247 kJ/mol, (stage I), 55-198 kJ/mol (stage II), and 64-148 kJ/mol (stage III) respectively. The corresponding entropy of activation falls in the range -100 to -260 J/K/mol (stage I), -181 to -294 J/K/mol (stage II),

109 in

the first stage, 22.52 to 5127479 in the second stage and 6.94

10-2

10-2 to

692.51 s-1 (stage I), 0.1209 to 15698.19 s-1 (stage II) and 1.09 10-2 to

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

191

and -245 to -291 J/K/mol (stage III). The pre-exponential factors are also seen varying from 0.1963 to 6.14 107 s-1 (stage I), 6.16 4219.76 s-1 (stage II), and 9.69 10-3 to 2.72 s-1 (stage III). The negative values for the entropies of activation indicate that the activated complexes have a more ordered structure than the reactants and the reaction are slower than the normal.(18-20) However, we could not identify any definite trends in the values for both Ea and S for the various adducts.

10-3 to

4.2.3 Mechanistic Aspects

The elucidation of mechanisms of solid-state thermal decomposition reaction is a complicated one. Several kinetic equations have been derived (Chapter 2) by various authors(21,22) for studying the mechanisms of the reactions corresponding to three possible types of rate determining steps during thermal decomposition, viz, nucleation and growth, diffusion and phase boundary reactions. The kinetic equations which govern the reaction mechanisms are based on the assumption that the form of g() depends on the reaction mechanisms, out of the nine forms of g() proposed by Satava (Chapter 2), the form of g() which gives the best representation of the experimental data is considered as the mechanism of the reaction. The correlation coefficients obtained for the nine forms of g() for the various stages of thermal decomposition of the complexes are presented in Tables 4.23-4.29 respectively.

192

Chapter 4

Table 4.23 Correlation coefficients calculated using the nine forms of g() for the Lewis-base adducts of nickel(II) and cobalt(II) succinates stage I
Form of g() [Ni(en)2(H2O)2] suc.2H2O -0.992313 -0.992955 -0.988506 [Ni(bipy)2(H2O)2] suc.2H2O -0.995600 -0.995819 -0.993842 [Ni(phen)2(H2O)2] suc.2H2O -0.997948 -0.997977 -0.996946 [Ni(py)(H2O) suc]n -0.974354 -0.974871 -0.937695 [Ni(pn)2suc]n [(Co(en)2 suc).H2O]n -0.992167 -0.992520 -0.988087 [Co(bipy)2(H2O)2] suc.2H2O -0.994446 -0.994773 -0.985945 [Co(phen)2] suc.2H2O -0.994384 -0.994445 -0.992617 [Co(py)2 suc]n -0.988945 -0.990252 -0.987206

2 +(1-) ln(1-) [1-(1-)1/3]2

-0.994034 -0.994054 -0.993257

2 (1- 3 )-(1-)2/3

-0.993210

-0.995841

-0.998014

-0.975039

-0.994180

-0.992621

-0.994863

-0.994481

-0.990783

-ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3

-0.993097 -0.989590 -0.982612 -0.991928 -0.992385

-0.995437 -0.993326 -0.988939 -0.995178 -0.995174

-0.997821 -0.996594 -0.994602 -0.997578 -0.997723

-0.964183 -0.901530 -0.543273 -0.962777 -0.963257

-0.993597 -0.992703 -0.991911 -0.993705 -0.993644

-0.991763 -0.987286 -0.978522 -0.991119 -0.991333

-0.993048 -0.980049 -0.863262 -0.992340 -0.992584

-0.993661 -0.991745 -0.989381 -0.993767 -0.993666

-0.992336 -0.991391 -0.990377 -0.990324 -0.990988

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

193

Table 4.24

Correlation coefficients calculated using the nine forms of g() for the Lewis-base adducts of nickel(II) and cobalt(II) succinates stage II
[Ni(en)2(H2O)2] suc.2H2O -0.985575 -0.985945 -0.980314 [Ni(bipy)2(H2O)2] suc.2H2O -0.981041 -0.981756 -0.978554 [Ni(phen)2(H2O)2] suc.2H2O -0.994073 -0.994191 -0.991511 [Ni(py)(H2O) suc]n -0.991261 -0.991325 -0.989544 [Ni(pn)2suc]n [(Co(en)2 suc).H2O]n -0.995766 -0.995922 -0.993292 [Co(bipy)2(H2O)2] suc.2H2O -0.990932 -0.990992 -0.987005 [Co(phen)2] suc.2H2O -0.997269 -0.997402 -0.997134 [Co(py)2 suc]n -0.992293 -0.992520 -0.984668

Form of g()

2 +(1-) ln(1-) [1-(1-)1/3]2

-0.998143 -0.998105 -0.997394

2 (1- 3 )-(1-)2/3

-0.986189

-0.982143

-0.994216

-0.991450

-0.998206

-0.995958

-0.991007

-0.997594

-0.992574

-ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3

-0.984788 -0.979619 -0.971596 -0.984046 -0.984270

-0.982379 -0.980239 -0.978241 -0.981192 -0.981555

-0.993324 -0.990182 -0.984662 -0.993202 -0.993272

-0.991082 -0.989406 -0.986874 -0.990639 -0.990943

-0.998068 -0.997202 -0.996293 -0.998026 -0.997976

-0.995313 -0.992916 -0.986377 -0.994961 -0.995188

-0.989562 -0.985198 -0.976357 -0.989424 -0.989438

-0.996558 -0.995717 -0.994674 -0.996967 -0.996873

-0.990296 -0.979621 -0.934995 -0.989913 -0.990126

194

Chapter 4

Table 4.25 Correlation coefficients calculated using the nine forms of g() for the Lewis-base adducts of nickel(II) and cobalt(II) succinates stage III
Form of g() [Ni(en)2(H2O)2] suc.2H2O -0.999107 -0.999151 -0.999073 [Ni(bipy)2(H2O)2] suc.2H2O -0.992787 -0.993395 -0.992270 [Ni(phen)2(H2O)2] suc.2H2O -0.994685 -0.994855 -0.994130 [Ni(pn)2suc]n [(Co(en)2 suc).H2O]n -0.993389 -0.993704 -0.977336 [Co(bipy)2(H2O)2] suc.2H2O -0.992130 -0.992301 -0.986120 [Co(phen)2] suc.2H2O -0.993547 -0.993702 -0.992235 [Co(py)2 suc]n -0.993338 -0.993446 -0.991883

2 +(1-) ln(1-) [1-(1-)1/3]2

-0.998655 -0.998623 -0.998239

(1- 3 )-(1-)2/3 -ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3

-0.999030

-0.993448

-0.994716

-0.998769

-0.993831

-0.992369

-0.993758

-0.993414

-0.999186 -0.998907 -0.998484 -0.999118 -0.998972

-0.993827 -0.992732 -0.991455 -0.993216 -0.993085

-0.995122 -0.994856 -0.994822 -0.994657 -0.994225

-0.998278 -0.997827 -0.997199 -0.998376 -0.998399

-0.990074 -0.958646 -0.338539 -0.989257 -0.989641

-0.990358 -0.981291 -0.952856 -0.989916 -0.990161

-0.993545 -0.992688 -0.990871 -0.993289 -0.993406

-0.992782 -0.991381 -0.989399 -0.992813 -0.992856

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

195

Table 4.26 Correlation coefficients calculated using the nine forms of g() for the Lewis-base adducts of nickel(II) and cobalt(II) succinates stage IV
Form of g() 2 +(1-) ln(1-) [1-(1-)1/3]2 (12 3

[Ni(en)2(H2O)2]suc.2H2O -0.985630 -0.985831 -0.982396 -0.985995 -0.985270 -0.981963 -0.977778 -0.984713 -0.984779

[Ni(bipy)2(H2O)2]suc.2H2O -0.991826 -0.992455 -0.991512 -0.992458 -0.992972 -0.992158 -0.991691 -0.992444 -0.992369

[Ni(phen)2(H2O)2]suc.2H2O -0.992725 -0.992966 -0.984462 -0.992980 -0.990644 -0.977203 -0.914307 -0.990189 -0.990172

[Co(bipy)2(H2O)2]suc.2H2O -0.985757 -0.986024 -0.974340 -0.986149 -0.982466 -0.966144 -0.921364 -0.981756 -0.982004

)-(1-)2/3

-ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3

196

Chapter 4

Table 4.27 Correlation coefficients calculated using the nine forms of g() for the Lewis-base adducts of copper(II) succinate stage I
Form of g() [Cu(en) suc]n [Cu(en)2(H2O)2] suc [Cu(bipy)suc]n [Cu2(phen)4suc] suc.12.5H2O -0.993222 -0.993632 -0.986048 [Cu(py)2suc]n [Cu(pn) suc]n [Cu (pn)2(H2O)2]suc -0.967122 -0.967785 -0.946753

2 +(1-) ln(1-) [1-(1-)1/3]2

2

-0.963314 -0.964061 -0.951625

-0.993331 -0.993397 -0.991295

-0.980040 -0.981528 -0.976792

-0.991539 -0.991852 -0.987659

-0.972986 -0.973390 -0.968529

(1- 3 )-(1-)2/3 -ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3

-0.964271

-0.993546

-0.981985

-0.993814

-0.991938

-0.973612

-0.968028

-0.960673 -0.947819 -0.928034 -0.959381 -0.959862

-0.992948 -0.990706 -0.986982 -0.992802 -0.992749

-0.983317 -0.981204 -0.977955 -0.981017 -0.981866

-0.992380 -0.982853 -0.949408 -0.991500 -0.991764

-0.991183 -0.987256 -0.980051 -0.990609 0.990730

-0.972525 -0.968319 -0.962879 -0.971691 -0.971848

-0.961417 -0.935182 -0.877039 -0.959915 -0.960425

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

197

Table 4.28 Correlation coefficients calculated using the nine forms of g() for the Lewis-base adducts of copper(II) succinate Stage II
Form of g() 2 +(1-) ln(1-) [1-(1-)1/3]2 (1- 3 )-(1-)2/3 -ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3
2

[Cu(en) suc]n -0.993042 -0.993149 -0.979781 -0.993183 -0.989496 -0.962202 -0.595524 -0.989263 -0.989215

[Cu(en)2(H2O)2] suc -0.983219 -0.983862 -0.965600 -0.984041 -0.979366 -0.954979 -0.861750 -0.978050 -0.978496

[Cu(bipy)suc]n -0.995278 -0.995432 -0.994274 -0.995491 -0.995261 -0.993490 -0.991253 -0.994863 -0.994996

[Cu2(phen)4suc] suc.12.5H2O -0.986372 -0.987902 -0.970268 -0.988412 -0.986962 -0.970303 -0.906577 -0.983913 -0.984953

[Cu(py)2suc]n 0.990336 -0.991086 -0.987824 -0.991304 -0.991467 -0.989287 -0.986177 -0.990400 -0.990723

[Cu(pn) suc]n -0.978888 -0.979219 -0.937593 -0.979345 -0.967366 -0.880062 -0.131269 -0.966347 -0.966794

[Cu(pn)2(H2O)2]suc -0.994195 -0.994604 -0.992067 -0.994718 -0.994610 -0.992688 -0.988537 -0.994079 -0.994297

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

199

Table 4.29 Correlation coefficients calculated using the nine forms of g() for the Lewis-base adducts of copper(II) succinate stage III
Form of g() 2 +(1-) ln(1-) [1-(1-)1/3]2 (12 3

[Cu(en)2(H2O)2] suc -0.994178 -0.994167 -0.988249 -0.994203 -0.991967 -0.981095 -0.918604 -0.992052 -0.991996

[Cu2(phen)4suc] suc.12.5H2O -0.984155 -0.984315 -0.975952 -0.984410 -0.981274 -0.970463 -0.946175 -0.980984 -0.981176

[Cu(pn)2 (H2O)2]suc -0.991861 -0.992118 -0.974579 -0.992207 -0.987742 -0.950268 -0.332144 -0.986891 -0.987322

)-(1-)2/3

-ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3

From the tables, it is evident that the form of g() with the
2/3, (three highest values of correlation coefficients is (1- 2 3 )-(1-)

dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation) in most cases, while in certain other cases the rate determining process is represented by g() = -ln(1-) corresponding to Random nucleation, one nucleus on each particle; obeying Mampel equation.(23,24) The forms of g() with the highest values of correlation coefficients for the various stages of decomposition of the complexes are given in Tables 4.30-4.40.

200

Chapter 4

Table 4.30 The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of nickel(II) succinate stage I
Compound [Ni(en)2(H2O)2] suc.2H2O [Ni(bipy)2(H2O)2] suc.2H2O [Ni(phen)2(H2O)2] suc.2H2O [Ni(py)(H2O)suc]n [Ni(pn)2suc]n Form of g()
2 3

Rate controlling process Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation

(1-

)-(1-)2/3

(1-

2 3

)-(1-)2/3

(1(1(1-

2 3

)-(1-)2/3 )-(1-)2/3 )-(1-)2/3

2 3 2 3

Table 4.31 The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of nickel(II) succinate stage II
Compound Form of g()
2 3

Rate controlling process Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Random nucleation, one nucleus on each particle, Mampel equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation

[Ni(en)2(H2O)2] suc.2H2O

(1-

)-(1-)2/3

[Ni(bipy)2(H2O)2] suc.2H2O

-ln(1-)

[Ni(phen)2(H2O)2] suc.2H2O

(1-

2 3

)- (1-)2/3

[Ni(py)(H2O)suc]n

(1-

2 3

)- (1-)2/3

[Ni(pn)2suc]n

(1-

2 3

)- (1-)2/3

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

201

Table 4.32 The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of nickel(II) succinate stage III
Compound Form of g() Rate controlling process Random nucleation, one nucleus on each particle, Mampel equation Random nucleation, one nucleus on each particle, Mampel equation Random nucleation, one nucleus on each particle, Mampel equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation

[Ni(en)2(H2O)2] suc.2H2O

-ln(1-)

[Ni(bipy)2(H2O)2] suc.2H2O

-ln(1-)

[Ni(phen)2(H2O)2] suc.2H2O

-ln(1-)

[Ni(pn)2suc]n

(1-

2 3

)-(1-)2/3

Table 4.33 The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of nickel(II) succinate stage IV
Compound Form of g() Rate controlling process Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Random nucleation, one nucleus on each particle, Mampel equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation

[Ni(en)2(H2O)2] suc.2H2O

(1-

2 3

)-(1-)2/3

[Ni(bipy)2(H2O)2] suc.2H2O

-ln(1-)

[Ni(phen)2(H2O)2] suc.2H2O

(1-

2 3

)-(1-)2/3

202

Chapter 4

Table 4.34 The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of cobalt(II) succinate stage I
Compound Form of g()
2 3

Rate controlling process Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Random nucleation, one nucleus on each particle, Mampel equation

[(Co(en)2suc).H2O]n

(1-

)-(1-)2/3

[Co(bipy)2(H2O)2] suc.2H2O

(1-

2 3

)-(1-)2/3

[Co(phen)2]suc.2H2O

(1-

2 3

)-(1-)2/3

[Co(py)2suc]n

-ln(1-)

Table 4.35 The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of cobalt(II) succinate stage II
Compound Form of g()
2 3

Rate controlling process Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation

[(Co(en)2suc).H2O]n

(1-

)-(1-)2/3

[Co(bipy)2(H2O)2] suc.2H2O

(1-

2 3

)-(1-)2/3

[Co(phen)2]suc.2H2O

(1-

2 3

)-(1-)2/3

[Co(py)2suc]n

(1-

2 3

)-(1-)2/3

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

203

Table 4.36 The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of cobalt(II) succinate stage III
Compound Form of g()
2 3

Rate controlling process Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation

[(Co(en)2suc).H2O]n

(1-

)-(1-)2/3

[Co(bipy)2(H2O)2] suc.2H2O

(1-

2 3

)-(1-)2/3

[Co(phen)2]suc.2H2O

(1-

2 3

)-(1-)2/3

[Co(py)2suc]n

(1-

2 3

)-(1-)2/3

Table 4.37 The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of cobalt(II) succinate stage IV
Compound [(Co(en)2suc).H2O]n Form of g() Rate controlling process Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation -

[Co(bipy)2(H2O)2] suc.2H2O

(1-

2 3

)-(1-)2/3

[Co(phen)2]suc.2H2O [Co(py)2suc]n

204

Chapter 4

Table 4.38 The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of copper(II) succinate stage I
Compound Form of g() Rate controlling process

[Cu(en)suc]n

2/3 (1- 2 3 )-(1-)

Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Random nucleation, one nucleus on each particle, Mampel equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation

[Cu(en)2(H2O)2]suc

2/3 (1- 2 3 )-(1-)

[Cu(bipy)suc]n

-ln(1-)

[Cu2(phen)4suc] suc.12.5H2O

2/3 (1- 2 3 )-(1-)

[Cu(py)2suc]n

2/3 (1- 2 3 )-(1-)

[Cu(pn)suc]n

2/3 (1- 2 3 )-(1-)

[Cu(pn)2(H2O)2]suc

2/3 (1- 2 3 )-(1-)

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

205

Table 4.39 The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of copper(II) succinate stage II

Compound

Form of g()

Rate controlling process Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Random nucleation, one nucleus on each particle, Mampel equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation

[Cu(en)suc]n

2/3 (1- 2 3 )-(1-)

[Cu(en)2(H2O)2]suc

2/3 (1- 2 3 )-(1-)

[Cu(bipy)suc]n

2/3 (1- 2 3 )-(1-)

[Cu2(phen)4suc] suc.12.5H2O

2/3 (1- 2 3 )-(1-)

[Cu(py)2suc]n

-ln(1-)

[Cu(pn)suc]n

2/3 (1- 2 3 )-(1-)

[Cu(pn)2(H2O)2]suc

2/3 (1- 2 3 )-(1-)

206

Chapter 4

Table 4.40

The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of copper(II) succinate stage III
Form of g() Rate controlling process Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation

Compound

[Cu(en)2(H2O)2]suc

(1-

2 3

)-(1-)2/3

[Cu2(phen)4suc] suc.12.5H2O

(1-

2 3

)-(1-)2/3

[Cu(pn)2(H2O)2]suc

(1-

2 3

)-(1-)2/3

4.2.4 Trend in thermal behaviour of metal succinates and their adducts

A look at the thermal decomposition temperature of parent metal succinates, shows that the succinate moiety decomposes from copper succinate easily than that in nickel and cobalt. The ease of decomposition order is [Cu(suc)]n (3000C)> [(Ni(H2O)2suc).2H2O]n (3550C) > [Co(suc)]n.2H2O (3700C). Such a trend is expected from the Irving-William series which suggests a stronger M-O bond in copper succinate that makes O-C bond of succinate moiety weaker. The thermal data associated with Lewisbase dissociation in the adducts of various metal succinates are shown in Table 4.41.

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

207

Among the adducts of nickel(II) succinate, the weakest metal Lewis-base bond is found to be Ni-N (pyridne) in 7. The overall trend found in the stability of the various nickel(II) succinate adducts from the decomposition of the first Lewis-base moiety is seen to be in the order 6 > 5 > 8 > 4 > 7. The activation energy, Ea associated with these thermal steps is also seen to be almost in the same order. The higher stability observed in pn adduct 8 than en adduct 4 is evident from their relative donor abilities. Such a trend is seen among the phen adduct and bipy adducts also. The S associated with the dissociation of one mole of Lewis-base found in en adduct 4, bipy adduct 5 and phen adduct 6 is seen to be more negative in 4 than in 5 and 6. This trend is quite anticipated from the Ea values associated with the thermal step (dissociation of one mole of Lewis-base). It may be noted that during the process of dissociation of this Lewis-base moiety, the non-bonded anionic succinate moiety could be getting coordinatively bound to the metal ion to satisfy its coordination requirement. Corresponding value for S for 7 is substantially more negative. The unusually very high negative value of S for py adduct 7 associated with the Lewis-base dissociation is also very consistent with the comparatively low Ea value for the process (Table 4.41). Among the adducts of cobalt(II) succinate, the weakest metal Lewis-base bond is found to be in py adduct 12 which is followed by bipy adduct 10 and phen adduct 11. The overall trend in the stability of various cobalt(II) succinate adducts from the decomposition of the first Lewis-base moiety (except in 9) is seen to be in the order 11 > 10 > 12. These values are consistent with the Ea values associated with the dissociation step. For the en

208

Chapter 4

adduct 9, we find the combined dissociation of both the en moieties in a single step. It is seen that the copper(II) succinate adducts exhibit almost similar thermal features as observed in the adducts of nickel(II) and cobalt(II) succinate. The pn adduct 19 is found to be stablest of all towards the initial Lewis-base dissociation. The thermal stability order for the dissociation steps is seen to be 19 > 14 > 20 > 18 > 17 > 15. It is interesting to note that in 15, 17 and 20 where the succinate moiety exists as non-coordinated ionic species, at the first Lewis-base dissociation steps itself, two ligand moieties are getting dissociated, making succinate moiety coordinated to the metal ion. The order in the activation energy, Ea found for them is 20 > 17 > 15. The S, seen for the process in 20 and in 15 are quite consistent with the trend. The non-consistent S value for 17 is evident from the fact that, the complex is dimeric in nature (see crystal and molecular structure, Section 3.3.12). In bipy adduct 16, we find that the decomposition involves the combined loss of Lewis-base and succinate moiety in a single step.

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

209

Table 4.41 Thermal data associated with Lewis-base dissociation in the adducts metal(II) succinates
Adducts Ti of fist Lewisbase loss (0C) 4 5 6 7 8 9 10 11 12 14 15 16 125 240 300 100 230 220 180 270 98 230 150 280* 170 180 240 200 Ti of second Lewis-base loss (0C) 235 270 280 145 Ti of final stage (0C) 350 300* 360* 355 350 360 360 335* 365 260 260 290* 260* 260 250 Ea (kJ/mol) S (J/K/mol)

[Ni(en)2(H2O)2]suc.2H2O [Ni(bipy)2(H2O)2]suc.2H2O [Ni(phen)2(H2O)2]suc.2H2O [Ni(py)(H2O)suc]n [Ni(pn)2suc]n [(Co(en)2suc).H2O]n [Co(bipy)2(H2O)2]suc.2H2O [[Co(phen)2]suc.2H2O [Co(py)2suc]n [Cu(en)suc]n [Cu(en)2(H2O)2]suc [Cu(bipy)suc]n

118.84 233.90 288.98 42.17 296.82 96.67 96.43 182.01 62.52 139.38 59.26 154.38* 63.70 107.80 247.64 125.90

-203.28 -109.94 -92.24 -279.20 -69.12 -236.97 -223.09 -170.44 -249.52 -199.77 -266.51 -177.52* -163.21 -218.43 -100.20 -206.12

[Cu2(phen)4(suc)]suc.12.5H2O 17 [Cu(py)2suc]n [Cu(pn)suc]n [Cu(pn)2(H2O)2]suc 18 19 20

* combined decomposition of Lewis-base + succinate moiety. Ea: S: activation energy associated with dissociation of first Lewis-base moiety entropy change associated with dissociation of first Lewis-base moiety

210

Chapter 4

References 1. E. V. Brusau, J. C. Pedregosa and G. E. Narda, J. Solid State Chem; 153 (2000) 1 2. 3. 4. J. L. Bear and C. T. Lin, J. Phy. Chem; 72 (1968) 2026 J. R. Allan and B. R. Carson, Thermochim Acta; 158 (1990) 91 K. M. A. Salaam, K. H. Halawani and S. A. Fakiha, Thermochim. Acta; 204 (1992) 311 5. 6. W. Bryzka and B. Galkowska, Polish. J. Chem; 72 (1998) 498 A. K. Nikumbh, S. K. Pardeshi and M. N. Raste, Therochim. Acta; 374 (2001) 115 7. Y. Suzuki, K. Muraishm and H. Ito, Thermochim. Acta; 258 (1995) 231 8. A. Venkataraman, V. A. Mukhedkar, M. M. Rahman, A. K. Nikumbh and A. J. Mukhedkar, Thermochim. Acta; 112 (1987) 231 9. U. B. Ceipidor, M. Tomassetti and E. Cardarelli, Thermochim. Acta; 30 (1979) 15 10. J. Masson, A. Busnot, F. Busnot and J. F. Hemidy, Thermochim. Acta; 122 (1987) 221 11. V. T. Yilmaz, S. Demir, O. Andac, W. T. A. Harrison, J. Coord. Chem; 55 (2002) 863

Thermal Dissociation Features of Succinate Complexes of Ni(II), Co(II) and Cu(II)..

211

12. 13.

W. W. Wendlandt, Anal. Chim. Acta; 17 (1957) 428 W. W. Wendlandt, Thermal Analysis, 3rd Ed., John Wiley and Sons, New York; (1986)

14. 15. 16. 17. 18.

A. W. Coats and J. P. Redfern, Nature; 201 (1964) 68 M. D. Juddo and M. T. Pope, J. Therm. Anal; 4 (1972) 31 J. Zsako, J. Therm. Anal; 5 (1973) 239 Y. M. Gorbechev, J. Therm. Anal; 8 (1975) 349 A. A. Froast and R. G. Pearson, Kinetics and Mechanism, Wiley, New York; (1961)

19.

T. Gangadevi, K. Muraleedharan and M. P. Kannan, Thermochim. Acta; 146 (1989) 225

20.

K. K. Aravindakshan and K. Muraleedharan, Thermochim. Acta; 155 (1989) 247

21. 22. 23.

J. Sestak and G. Berggren, Thermochim. Acta; 3 (1971) 1 V. Satava, Thermochim. Acta; 2 (1971) 423 C. G. R. Nair, S. Mathew and K. N. Ninan, Thermochim. Acta; 150 (1989) 63

24.

S. Mathew, C. G. R. Nair and K. N. Ninan, Thermochim. Acta; 144 (1989) 33

Chapter 5 Interaction of Lewis-bases with Polymeric Metal(II) Malonates

5.1

bound to a sp3 hybridised C, the coordination of the two carboxylate moieties can, in principle, keep the bound metal ions at a distance as close as 3 (if the coordination is anti-anti inward) and can also dispose metal atoms quite away at >5 (if the coordination is anti-anti, outward). Like in the case of succinate systems the carboxylate moieties in malonate do not have any conjugative connection through the spacer function. Consequently the -COO moieties can exhibit the same type of bonding features as in the succinate systems through both the functional ends. However, there is an unique bonding feature possible specifically in the case of metal malonates wherein the malonates can bind in bidentate chelating manner through one O each of the carboxylate groups to form a six-membered metallocycle. Metal malonate framework involving rare-earth metal ions have been shown to possess interesting properties.(1,2) An essential feature in most of these structures is that the malonate ions participate in the skeleton along with the inorganic species, acting both as part of the extended oxide chains or sheets and as pillars between the latter, which is in contrast to the metal where isolated La system, organic framework compounds of Yaghi et al, has reported an interesting dinuclear

Introduction
ompared to succinic acid, the malonic acid, (H2mal), HOOC-CH2-COOH, has one -CH2- function between the two carboxylic groups. Since the -COOH function is

metal clusters are connected by organic linkers.(3) Benmerad et al(4) [La(mal)3(H2O)4].H2O which has been shown to have a layer-type

212

Chapter 5

polymeric doubly

structure

and

has The

one 3D

malonate structure

group seen

as in

monodentate and triply bridging chelating while the other as monodentate. K3[Be3(OH)3(mal)3].6H2O(5), [SrM(mal)2(H2O)5].2H2O(6) (M = Mn, Fe, Co, Ni) and [Na2Ni(mal)2(H2O)6]n(7) are also particularly interesting. Equally interesting one is cadmium malonate, [Cd(mal)(H2O)].H2O(8) with infinite Cd-O-Cd connectivity having hydrophobic channels lined with methylene groups. Some square grid network systems, [MnCu(mal)2(H2O)4].2H2O(9) and [Cu2(mal)2(H2O)2(4,4'-bipy)](10) with two-dimensional structure have also been reported. In these framework systems the malonato group acts simultaneously as bidentate and monodentate moieties leading to a bimetallic chain and the bridging carboxylate function is seen to exhibit an anti-syn coordination mode. Several other interesting mixed ligand malonato complexes with 1D chain(11-17) and 3D(18-21) framework structures have also been reported. Zhang et al(22) reported an interesting system, [M(mal)2(SC(NH2)2)2]n (M = Cd or Zn), which has been shown to have a helical structure wherein the malonate dianion acts as a bidentate ligand coordinated with metal ions to form the back bone of the helix. Interesting antiferromagnetic behaviour was seen in many of metal malonates of Fe, Co, Ni and Cu systems.(6,7,13,16) Recently Cuevas et al,(23) reported heterobimetallic complexes, [ReCl4(mal)Cu(L)2].CH3CN (L = phen, bipy), in which the malonate dianion functions either in bridging mode or as a bidentate chelating ligand. There are reports of malonate crown ethers used as building blocks(24) and some allyl and diallyl derivatives of malonates are shown to exhibit interesting catalytic properties.(25) The present chapter deals with the synthesis and structural features of some of the metal malonates and a

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

213

systematic study of their interaction with various Lewis-bases and the investigation on the structural features of the resulting mixed ligand complexes.

5.2

Experimental

5.2.1 Preparation of metal(II) malonates (a) Nickel(II) malonate complex, [Ni(H2O)2(mal)]n, 21 To an aqueous solution of malonic acid (0.11g, 1mM), nickel(II) carbonate (0.37g, 1mM) was added slowly with stirring. The reaction mixture was boiled on a steam bath for about 1 h. The amount of nickel carbonate added was slightly less than the stoichiometric amount of malonic acid. The green complex formed was filtered and washed repeatedly with hot water to remove any excess of malonic acid present and finally with methanol. The pure complex thus obtained was dried under vacuum over P2O5. (yield : 90%) (b) Cobalt(II) malonate complex, [Co(H2O)2(mal)]n, 22 The preparative procedure adopted for this complex was almost the same as that of nickel(II) malonate complex. About 0.12g (1mM) of cobalt carbonate was added in small quantity to a hot aqueous solution of 0.11g malonic acid (1mM) while stirring. The reaction mixture was boiled on a waterbath. The pink complex formed was filtered and washed repeatedly with hot water and finally with methanol. The pure complex thus obtained was dried in vacuo. (yield : 85%) (c) Copper(II) malonate complex, [Cu(H2O)2(mal)]n, 23 About 0.23g (1mM) of cupric carbonate was added in small quantity with stirring to a hot aqueous solution of malonic acid

214

Chapter 5

(0.11g, 1mM). The amount of cupric carbonate was kept slightly greater than the stoichiometric amount of malonic acid. Unlike nickel(II) and cobalt(II) malonate a clear blue solution was obtained on the addition of the metal salt into the malonic acid solution. A pinch of excess cupric carbonate was added to the clear solution obtained to check the completion of reaction. Any excess cupric carbonate present was removed by repeated filtration. The complex was separated by concentrating the filtrate on a steam bath and it was purified by recrystallisation from hot water. The blue complex obtained was dried under vacuum. (yield : 85%) 5.2.2 Preparation of Lewis-base adducts of nickel(II) malonate (a) [Ni(en)2(H2O)2]mal, 24 A solution of en (0.13ml, 2mM) in methanol was added dropwise to a suspension of nickel(II) malonate (0.19g, 1mM) in methanol with constant stirring for about half an hour. A clear violet solution was obtained which was filtered and concentrated to half of its volume and cooled. The complex was separated as violet solid and was filtered. This was repeatedly washed with ether and dried under vacuum over P2O5. (yield: 80%) (b) [Ni(bipy)2(H2O)2]mal, 25 About 0.31g (2mM) of 2,2'-bipy was dissolved in 10 ml of methanol and was added dropwise to a suspension of nickel(II) malonate (0.19g, 1mM) in methanol. This was kept under reflux for about 30 min. A clear light violet solution was obtained which was filtered and then concentrated to half of its volume and cooled. The complex separated out as light violet solid which was

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

215

then filtered. This was repeatedly washed with ether and dried in vacuo. (yield :80%) (c) [Ni(phen)2mal].3H2O, 26 The method adopted for the preparation of this compound was almost similar to that employed for the 2,2'-bipyridine adduct. The clear light violet solution obtained after reflux with 0.4g (2mM) of phen for about 30 min which was concentrated to half of its volume and cooled. The complex gets precipitated as light violet solid which was filtered. It was repeatedly washed with ether and dried in vacuo. (yield :85%) (d) (Ni(py)(H2O)mal]n, 27 A solution of pyridine (0.48ml, 3mM) was added to a nickel(II) malonate (0.39g, 1mM) suspension in methanol with constant stirring. The reaction mixture was refluxed for about 2 h. The colour change of the parent complex gives a clear indication of the formation of the new adduct. The light green complex formed was separated out by filtration. It was repeatedly washed with methanol followed by ether. This was dried in vacuo. (yield :75%) (e) [Ni(pn)2(H2O)2]mal.2H2O, 28 A solution of pn (0.34ml, 2mM) in methanol was added dropwise to a suspension of nickel(II) malonate (0.39g, 1mM) in methanol with constant stirring for about 1 h. A clear dark blue solution was obtained which was filtered and concentrated to half of its volume and then cooled. The complex separated out as a dark blue solid was filtered. This was repeatedly washed with acetone and dried under vacuo. (yield :85%)

216

Chapter 5

5.2.3 (a)

Preparation of Lewis-base adducts of cobalt(II) malonate [(Co(en)2mal).H2O]n,, 29 A solution of en (0.13ml, 2mM) in methanol was added to a

suspension of cobalt(II) malonate (0.19g, 1mM) in methanol with constant stirring for about 1 h. A clear brown solution was obtained which was filtered and was concentrated to half of its volume. On cooling, a pasty mass was obtained which on stirring with ether light brown complex was separated. It was filtered and washed repeatedly with ether and dried in vacuo. (yield :70%) (b) [Co(bipy)2(H2O)2]mal, 30 To a suspension of cobalt(II) malonate (0.39g, 1mM) in methanol, a solution of 2,2'-bipy in methanol (0.62g, 2mM) was added. The mixture was kept under reflux for 2 h. A clear orange solution was obtained which was filtered and concentrated to half of its volume and then cooled. The orange complex was separated out by filtration. It was washed repeatedly with ether to obtain the pure complex and dried under vacuum over P2O5. (yield :85%) (c) [Co(phen)2(H2O)2]mal, 31 The method adopted for the preparation of this adduct was almost similar to that employed for the 2,2'-bipyridine adduct. A clear orange solution was obtained after reflux with 0.4g (2mM) of phen which was filtered and concentrated to half of its volume and then cooled. The orange complex was separated out by filtration. It was washed repeatedly with ether and dried in vacuo. (yield :85%) (d) [Co(py)(H2O)mal]n, 32 A solution of pyridine (0.48ml, 3mM) in methanol was added to a cobalt(II) malonate (0.39g, 1mM) suspension in methanol with

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

217

constant stirring. Suddenly the colour of the complex changed from pink to rose. The reaction mixture was refluxed for about 3 h. The rose coloured complex was separated out by filtration. It was washed repeatedly with hot methanol followed by diethyl ether. The complex was finally dried in vacuo. (yield : 80%) (e) [(Co(pn)2mal).H2O]n, 33 A solution of pn (0.18ml, 2mM) in methanol was added dropwise to a suspension of cobalt(II) malonate (0.19g, 1mM) in methanol with constant stirring for about 1 h. A clear dark brown solution was obtained which was concentrated to half of its volume and then cooled. A pasty mass was obtained which on stirring with acetone brown complex was separated. It was filtered and repeatedly washed with acetone. This was dried in vacuo. (yield : 70%) 5.2.4 Preparation of Lewis-base adducts of copper(II) malonate (a) [Cu(en)mal], 34 A solution of en (0.13ml, 1mM) in methanol was added dropwise to a suspension of copper(II) malonate (0.4g, 1mM) in methanol with constant stirring for about 2 h. A clear dark blue solution was obtained which was filtered and concentrated to half of its volume and then cooled. The dark blue complex formed was separated out by filtration and was purified by washing several times with diethyl ether. It was dried in vacuo. (yield : 85%) (b) [Cu(en)2]mal.H2O, 35 A solution of en (0.13ml, 2mM) in methanol was added dropwise to a suspension of copper(II) malonate (0.2g, 1mM) with constant stirring for about 30 min. A clear dark violet solution was

218

Chapter 5

obtained which was filtered and concentrated to half of its volume and then cooled. The violet complex formed was separated out by filtration and was purified by washing several times with ether. The compound was dried under vacuum over P2O5. (yield : 85%) (c) [Cu(bipy)(mal)H2O].H2O, 36 A solution of 2,2'-bipy in methanol (0.62g, 2mM) was added dropwise to a suspension of copper(II) malonate (0.4g, 1mM) in methanol with constant stirring. The mixture was kept under reflux for about half an hour. A clear blue solution was obtained which was filtered and concentrated to half of its volume and then cooled. The blue crystals formed were separated out by filtration and purified by washing several times with ether. This was dried in vacuum. (yield : 85%) (d) [Cu(phen)2]mal.2H2O, 37 To a suspension of copper(II) malonate (0.2g, 1mM) in methanol, a solution of 0.4g (2mM) of phen dissolved in 15ml methanol was added with stirring. The reaction mixture was kept under reflux for about 30 min when the solution turned green. It was filtered and was concentrated to half of its volume and cooled. The green complex formed was separated out by filtration and was washed repeatedly with ether to obtain the pure complex. This was dried in vacuo. (yield : 85%)

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

219

(e)

[Cu(py)(H2O)mal]n, 38 A solution of pyridne (0.48ml, 3mM) in methanol was added to

a copper(II) malonate suspension (0.4g, 1mM) in methanol with stirring. The reaction mixture was refluxed for about 3 h. The blue complex formed was separated out by filtration and was washed several times with hot methanol followed by ether. It was dried under vacuum over P2O5. (yield : 80%) (f) [Cu(pn)2]mal.2H2O, 39 A solution of pn (0.34ml, 2mM) in methanol was added dropwise to a suspension of copper(II) malonate (0.4g, 1mM) in methanol with constant stirring for about 1 h. A clear violet solution was obtained which was filtered and was concentrated to half of its volume and then cooled. The complex was separated out as violet solid and was filtered. This was washed repeatedly with acetone and dried in vacuo. (yield : 85%) 5.3.

Results and Discussion

The preparative procedure adopted for generating metal(II)

5.3.1. Metal malonates of Ni(II), Co(II) and Cu(II) malonates is same as that of metal(II) succinates which are described in Chapter 3. Analysis of the various metal(II) malonates were carried out for C, H, N content by Heraeus CHN rapid analyser and for the metal by known procedures. The data show a strict 1:1 composition (metal: mal) for all the malonate complexes of divalent metal ions (Table 5.1). The composition of various metal(II) malonates were found to be agreeing to [M(H2O)2(mal)]n where M = Ni(II), Co(II) and Cu(II). The amount of water present in the various metal(II) malonates could be checked by TG analysis and the data obtained are seen to be consistent with the compositions indicated in Table 5.1.

220

Chapter 5

Table 5.1. Elemental analytical data of metal(II) malonates

Complex (Emp. formula) [Ni(H2O)2mal]n (NiC3H6O6) 196.69 18.32 (18.30) 3.10 (3.07) 29.9 (29.8) Green Formula weight Elemental content (%) obsvd (calcd) C H M

Colour

21
[Co(H2O)2mal]n (CoC3H6O6 ) 196.93 18.30 (18.28) 3.10 (3.07) 30.0 (29.9) Pink

22
[Cu(H2O)2mal] (CuC3H6O6 ) 201.54 17.90 (17.86) 2.98 (3.00) 31.6 (31.5) Blue

23

The characteristic broad band at 3075 cm-1 due to (O-H) in the free ligand H2(mal) was found to be absent in all the metal(II) malonate complexes. This indicates the existence of deprotonated form of the malonate group in the metal complexes. However, broad peaks in the range 3260-3230 cm-1 were seen in all the complexes which are characteristic of (O-H) band of H2O indicating the presence of water in the system. The typical carboxylate peaks as(CO2) and s(CO2) of the malonic acid are seen to occur at 1706 and 1460 cm-1 respectively in these metal malonates. The coordination modes of carboxylate groups could be determined by noting the separation ( ) between as(CO2) and s(CO2) which are already mentioned in Chapter 3. For the present metal(II) malonates these two peaks are seen to be at 1621, 1451 cm-1 for 21, 1618, 1450 cm-1 for 22 and 1602, 1370 cm-1 for 23 (Table 5.2). The lower values observed for the metal malonates compared to 246 cm-1 of malonic acid indicates

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

221

the symmetric nature of the carboxylate group in the complexes suggesting the chelating character of the -COO- moiety.(26-28) For 23, the value is comparatively much higher than that for 21 and 22. This indicates that the carboxylate group in 23 is bonded to copper in a monodentate fashion.(29-30) Table 5.2. Important IR spectral data of metal(II) malonates (cm-1)
Compound H2mal [Ni(H2O)2mal]n 21 [Co(H2O)2mal]n 22 [Cu(H2O)2mal] 23 (O H) 3075 3260 3240 3230 (O H) 1605 1610 1598 1600 as(CO2) 1706 1621 1618 1602 s(CO2) 1460 1451 1450 1370 246 170 168 232

As in the case of metal succinates, the electronic spectra of metal malonates also could be recorded only in the solid state because of their insolubility. The assignment of the various transitions associated with the absorption maxima are given in Table 5.3. Nickel(II) malonate, 21, gave three peaks at 25250, 15220 and 10470 cm-1 which are typical of octahedral Ni(II).( 31,32) In the case of cobalt(II) malonate, 22, the absorption peaks were seen at 19340 and 14380 cm-1. This is also very characteristics of octahedral Co(II) species.(33,34) The broad absorption band for copper(II) malonate, 23, observed at 13670 cm-1 is characteristic of four coordinated form with almost square planar structure for the complex.(35-37) Table 5.3. Electronic spectral and magnetic data of metal(II) malonates
Compound Abs. max

(cm-1)

Assignments

eff (BM)

222

Chapter 5

10470

3A 3A 3A

2g(F) 2g(F) 2g(F) 4T 1g

3T2g(F) 1 3T1g(F) 2 3T1g(P) 3 4T1g(P) 4 A2g 2 A1g 1.64 2.97

21

15220 25250 19340

22
14380

4.53

4T 1g 2B

23

13670

1g

Magnetic measurements showed that all the above malonate complexes are paramagnetic in nature. The observed values of eff values for the complexes are given in the above table. Both Ni(II) and Co(II) malonates exist as high-spin species rather than as low spin species. All the foregoing data indicate the strict sixcoordinated character for Ni(II) and Co(II) whereas four coordinated character for Cu(II) malonate. Based on the above observations and high insolubility of the malonates the overall structure of malonate complexes could be considered as polymeric in nature with both the carboxylate groups chelatively bidentating for 21 and 22 and monodentatively coordinating in 23.

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

223

5.3.2 Lewis-base mediated fragmentation of polymeric nickel(II) malonate The set of Lewis-bases chosen for the interaction studies with polymeric nickel(II) malonate, were the same as those used for metal succinate system. We have carried out the interaction of Lewis-bases with Ni(II), Co(II) and Cu(II) malonates under various reaction conditions and stoichiometric proportions. However, to isolate the new structural species we have employed some optimum reaction conditions. These along with some salient features of the reactions and products isolated are presented in Table 5.4. As indicated in Table 5.4 and in the preparative section, the adduct formation and breaking up of the polymeric network occur with comparative ease with en, bipy, phen and pn at the addition of the ligand itself. However, py does not seem to depolymerise the metal malonates. The analytical data shown in Table 5.5 confirm the 1:2 (nickel malonate: Lewis-base) composition for en, bipy, phen and pn complexes and 1:1 composition for py complex.

224

Chapter 5

Table 5.4 Interaction of metal(II) malonates with various Lewis-bases(LB)

Metal malonate +LB (in MeOH) 21 + en (1:1) 21 + en (1:2) 21 + bipy (1:1) 21 + bipy (1:2) 21 + phen (1:1) 21 + phen (1:2) 21 + py (1:1) 21 + py (1:2) 21 + (py excess) 21 + pn (1:1) 21 + pn (1:2) 22 + en (1:1) 22 + en (1:2) 22 + bipy (1:1) stirring, RT, (2h) stirring, RT, (1h) stirring under reflux, (2h) stirring under reflux, (1h) stirring under reflux, (2h) stirring under reflux, (1h) stirring under reflux, (3h) stirring under reflux, (3h) stirring under reflux, (3h) stirring, RT, (2h) stirring, RT, (1h) stirring, RT, (2h) stirring, RT, (1h) stirring under reflux, (2h) partial dissolution to give light violet solution complete dissolution (clear violet solution) partial dissolution (light violet solution) complete dissolution (clear light violet solution) partial dissolution (light violet solution) complete dissolution (clear light violet solution) no observable change slight colour change from green to light green (incomplete reaction) colour change from green to light green partial dissolution (light blue solution) complete dissolution (clear dark blue solution) partial dissolution (light brown solution) complete dissolution (clear dark brown solution) partial dissolution (light orange solution) [(Co(en)2mal).H2O]n (29) [Ni(H2O)(py)mal]n. (27) [Ni(phen)2mal].3H2O (26) [Ni(bipy)2(H2O)2]mal (25) no stoichiometric compound [Ni(en)2(H2O)2]mal (24) Conditions Observation Products Separated

no characterisable product

no stoichiometric compound

no characterisable product

no stoichiometric compound

no characterisable product [Ni(pn)2(H2O)2]mal.2H2O (28) no stoichiometric compound

no characterisable product

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

225

22 + bipy (1:2) 22 + phen (1:1) 22 + phen (1:2) 22+py (1:1) 22+py (1:2) 22+(py excess) 22 + pn (1:1) 22 + pn (1:2) 23 + en (1:1) 23 + en (1:2) 23 + bipy (1:1) 23 + bipy (1:2) 23 + phen (1:1) 23 + phen (1:2)

stirring under reflux, (1h) stirring under reflux, (2h) stirring under reflux, (1h) stirring under reflux, (3h) stirring under reflux, (3h) stirring under reflux, (3h) stirring, RT, (2h) stirring, RT, (1h)

complete dissolution (clear orange solution) partial dissolution (light orange solution) complete dissolution (clear orange solution) no observable change slight colour change (from pink to rose) colour change from pink to rose (solution colourless) partial dissolution (light brown solution) complete dissolution (clear dark brown solution) complete dissolution (clear dark blue solution) complete dissolution (clear dark violet solution) complete dissolution (clear light blue solution) complete dissolution (clear light blue solution) complete dissolution (clear blue solution) complete dissolution (clear green solution)

[Co(bipy)2(H2O)2]mal

(30)

no characterisable product [Co(phen)2(H2O)2]mal (31)

no stoichiometric compound

no characterisable product

[Co(py)(H2O)mal]n

(32)

no stoichiometric compound

[(Co(pn)2mal).H2O]n

(33)

stirring, RT, (2h)

[Cu(en)mal]

(34)

stirring, RT, (1h)

[Cu(en)2]mal.H2O

(35)

stirring under reflux, (2h) stirring under reflux, (1h) stirring under reflux, (2h) stirring under reflux, (1h)

[Cu(bipy)(H2O)mal].H2O (36)

[Cu(phen)2]mal.2H2O

(37)

23 + py

stirring under

no observable change

no stoichiometric compound

226
reflux, (3h) slight colour change from blue to intense blue (incomplete reaction) colour change from blue to intense blue (solution colourless) complete dissolution (clear dark blue solution) complete dissolution (clear dark violet solution)

Chapter 5

(1:1) 23 + py (1:2) 23+ (py excess) 23 + pn (1:1) 23 + pn (1:2)

stirring under reflux, (3h)

product mixture

stirring under reflux, (3h)

[Cu(py)(H2O)mal]n

(38)

stirring, RT, (2h)

stirring, RT, (1h)

[Cu(pn)2]mal.2H2O

(39)

Table 5.5 Elemental analytical data of Lewis-base adducts of metal(II) malonates

Complex (Emp. Formula) [Ni(en)2(H2O)2]mal NiC7H22O6N4 (24) [Ni(bipy)2(H2O)2]mal NiC23H22O6N4 (25) [Ni(phen)2mal].3H2O NiC27H28O9N4 (26) [Ni(py)(H2O)mal]n NiC8H9O5N (27) [Ni(pn)2(H2O)2]mal.2H2O NiC9H30O8N4 (28) [(Co(en)2mal).H2O]n CoC7H20O5N4 (29) [Co(bipy)2(H2O)2]mal 509.31 298.93 380.95 257.79 611.15 509.07 Formula weight Elemental content % obsvd (calcd) C 26.55 (26.52) H 6.98 (7.00) N 17.70 (17.68) M 18.6 (18.5) Violet Colour

316.69

54.30 (54.21)

4.40 (4.35)

10.98 (11.00)

11.6 (11.5)

Light violet

53.05 (53.01)

4.60 (4.62)

9.20 (9.16)

9.7 (9.6)

Light violet

37.27 (37.23)

3.60 (3.51)

5.50 (5.43)

22.8 (22.7)

Green

28.40 (28.35)

8.00 (7.93)

14.75 (14.70)

15.5 (15.4)

Dark blue

28.05 (28.10) 54.21

6.75 (6.74) 4.30

18.70 (18.73) 10.95

19.8 (19.7) 11.6

Brown Yellowish

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

227
(10.99) (11.5) orange

CoC23H22O6N4 (30) [Co(phen)2(H2O)2]mal CoC27H26O8N4 (31) [Co(py) (H2O)mal]n CoC8H9O5N (32) [(Co(pn)2mal).H2O]n CoC9H24O5 N4 (33) [Cu(en)mal] CuC5H10O4N2 (34) [Cu(en)2]mal.H2O CuC7H20O5N4 (35) [Cu(bipy)(mal)H2O] .H2O CuC13H14O6N2 (36) [Cu(phen)2]mal.2H2O CuC27H26O8N4 (37) [Cu(py)(H2O)mal]n CuC8H9O5N (38) [Cu(pn)2]mal.2H2O CuC9H26O6N4 (39) 349.74 262.64 598.00 357.73 303.54 225.54 327.19 258.03 593.39

(54.19)

(4.35)

54.55 (54.60)

4.40 (4.41)

9.50 (9.43)

9.8 (9.9)

Yellowish orange

37.18 (37.20)

3.55 (3.51)

5.40 (5.42)

22.9 (22.8)

Rose

32.95 (33.00)

7.40 (7.39)

17.15 (17.11)

17.9 (18.0)

Brown

26.62 (26.60)

4.50 (4.46)

12.40 (12.41)

28.2 (28.1)

Dark blue

27.70 (27.67)

6.60 (6.64)

18.48 (18.45)

21.0 (20.9)

Violet

43.62 (43.60)

3.96 (3.94) 4.40 (4.38) 3.40 (3.45)

7.80 (7.82)

17.8 (17.7)

Blue

54.20 (54.18)

9.30 (9.36)

10.7 (10.6)

Green

36.60 (36.55)

5.30 (5.33)

24.2 (24.1)

Blue

30.90 (30.88)

7.40 (7.49)

16.10 (16.01)

18.2 (18.1)

Dark blue

228

Chapter 5

5.3.3 IR spectra of Lewis-base adducts of nickel(II) malonate The presence of Lewis-bases in all the adducts of nickel(II) malonate, 21, obtained by the fragmentation process by Lewis-base attack is confirmed by their characteristic peaks in the IR spectra. The as(CO2) stretching band occurring at 1621 cm-1 in 21 was found shifted to the lower region 1570-1615 cm-1 in its 1398-1449 cm-1 in them. In the IR spectra of the adduct 24, 25 and 28, the carboxylate moieties of the malonate groups have vibrational modes and (146 cm-1 for 24, 156 cm-1 for 25 and 141 cm-1 for 28) characteristic of ionic malonate. For the adduct 26, the as(CO2) and s(CO2) bands of the carboxylate moiety were observed at 1613 and 1398 cm-1 respectively with a of 215 cm-1 indicating that the carboxylate group is bonded to metal in a monodentate manner. However, in the adduct 27, the carboxylate vibrations were seen at 1615 and 1449 cm-1 with a of 166 cm-1 which is characteristic of bidentate chelating nature of the carboxylate groups in them. All the other relevant IR absorption frequencies of nickel(II) malonate and their adducts including those of the Lewis-base moieties are given in Table 5.6. We have monitored the trend in the changes of both asymmetric and symmetric stretching frequencies in the adducts. The order noticed (Table 5.6) for among the various adducts are seen to be 26 > 27 > 25 > 24 > 28. The trend as discussed in Chapter 3 is seen to be dependent on the pKa values of the various Lewis-bases used and the reason could be attributed to the relative adducts and s(CO2) stretching band observed at 1451 cm-1 was found lowered to

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

229

electronic charge accumulation on the metal centre caused by the coordinating Lewis-base which then gets partially transferred to the * orbitals of the carboxylate moiety through back donation, making the conjugative bond of the carboxylate moiety weaker. The consequence is the substantial reduction in the COO based stretching frequencies and also . Table 5.6 IR spectral data of nickel(II) malonate and its various Lewis-base adducts isolated (cm-1)
Adducts (O-H) as(CO2) s(CO2) (C-O) 21 3260 1621 1451 170 1376 24 3280 1572 1426 146 1341 1025 3353 3293 1580 715 528 25 3278 1596 1440 156 1359 1625 1450 769 1019 460 648 452 636 482 705 26 3365 1613 1398 215 1330 1613 1470 724 27 3240 1615 1449 166 1349 1604 1472 28 3424 3270 1570 1429 141 1348 1020 3310 3281 1610 660 478 -

C C C N
(C-N) (C-H) (C-H) (NH2) (NH2) NH2 wag MN stret Ring deformation (outplane) (inplane)

230

Chapter 5

5.3.4 Electronic spectra and magnetic data of Lewis-base adducts of nickel(II) malonate The electronic spectra of all the adducts of nickel(II) malonate were recorded either in solid state or in solution (methanol) state. Some of the spectra are reproduced in Fig.5.1. The characteristic features in the bands of 21, are seen to be getting modified in all their adducts indicating structural modifications on adduct formation. The absorption bands were observed in the region 25640-27620 cm-1, 15600-17920 cm-1 and 10630-11860 cm-1 in its adducts. These could be assigned to 3A2g(F) 3T1g(P) (3);
3A 2g(F)

3T

1g(F)

(2); and

3A

2g(F)

3T

2g(F)

(1) respectively in We have

agreement with typical Ni(II) octahedral complex.(31,32)

evaluated the ligand-field parameters Dq, the Racah parameter (B) and Nephelauxetic parameter () for the various adducts using reported procedure.(38) The evaluation method were the same as used for the adducts of nickel(II) succinates. The Dq values among the adducts were seen to decreases in the order 28 > 24 > 25 > 26 > 27. The trend is seen to be dependent on the pKa value of the various Lewis-bases (Table 5.7).

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

231

Fig 5.1 Electronic spectra of nickel(II) malonate and its Lewis-base adducts a) [Ni(H2O)2(mal)]n,

21

d) e) f)

[Ni(phen)2mal].3H2O, [Ni(py)(H2O)mal]n,

26 27

b) [Ni(en)2(H2O)2]mal, 24 c) [Ni(bipy)2(H2O)2]mal, 25

[Ni(pn)2(H2O)2]mal.2H2O, 28

232

Chapter 5

Table 5.7. Electronic spectral and magnetic moment data of Lewisbase adducts of nickel(II) malonate
Adducts Absorption max

(cm-1)

Assignments*

Dq (cm-1)

B (cm-1)

2/1

eff
(BM)

10470 21 15220 25250 11320 24 17920 27620 11010 25 17760 26180 10920 26 17890 26040 10630 27 15600 25640 11860 28 17390 27550

1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3
3A 2g

1047

0.62

604

1.45

2.97

1132

0.71

772

1.58

3.14

1101

0.65

727

1.61

3.16

1092

0.63

745

1.64

3.17

1063

0.64

623

1.47

3.05

1186

0.61

624

1.47

3.10

3A 2g

3T2g(F) (1),

3T1g(F) (2),

3A 2g

3T1g(P) (3)

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

233

The eff values evaluated for all the Ni(II) adducts are found to be in the range 3.05-3.17 BM which are in agreement with the values expected for octahedral complexes. Based on the elemental analysis, IR, electronic and magnetic moments studies, all the adducts of nickel(II) malonate isolated are found to have the octahedral structure. The adduct 24, 25 and 28 are found to be octahedral with ionic malonates whereas the adduct 26, is seen to have the octahedral structure with monodentate linkage of malonate function. However, the adduct 27, is found to be polymeric octahedral with bidentate chelation of malonate moiety. This was further evident from their values of the carboxylate moiety. 5.3.5 Lewis-base mediated fragmentation of polymeric cobalt(II) malonate The depolymerisation and coordination expansion of the cobalt(II) malonate, 22, was attempted by employing the same set of Lewis-bases used for nickel(II) malonate system. Though various reaction conditions were employed, we have focussed our study in methanol solvent. Several mixed ligand complexes could be isolated by depolymerisation and coordination sphere expansion of 22. The details are already presented in Table 5.4. The analytical data shown in Table 5.5 confirm the 1:2 composition (cobalt malonate: Lewisbase) for all the adducts except for that of pyridine. 5.3.6 IR spectra of Lewis-base adducts of cobalt(II) malonate As compared to the IR spectra of cobalt(II) malonate, its Lewisbase adducts gave several additional and modified peaks. The additional peaks in all the cases correspond to the Lewis-base moiety present in each of the complex. The as(CO2) and s(CO2) stretching bands occurring at 1618 and 1450 cm-1 in compound 22 were found

234

Chapter 5

shifted to lower regions 1557-1611 cm-1 and 1327-1445 cm-1 respectively in its adducts. On examining the IR spectra of the adducts 29 and 33 the as(CO2) and s(CO2) bands were observed at 1557, 1327 cm-1 (29) and 1578, 1350 cm-1 (33) respectively. The values are seen to be characteristic of monodentate nature of carboxylate groups in them ( for 29 is 230 cm-1 and for 33 it is 228 cm-1). carboxylate group were observed at 1597, 1441 cm-1 But in the (30) and

IR spectra of the adducts 30 and 31, the corresponding bands of 1598, 1440 cm-1 (31) respectively. The values (156 cm-1 for 30 and 158 cm-1 for 31) clearly show the non-bonded nature of carboxylate group in them. However, in the adduct 32, the as(CO2) and s(CO2) bands were observed at 1611 and 1445 cm-1 with a value of 166 cm-1 which is characteristic of bidentate chelating nature of carboxylate group in them. The order noticed for among the various adducts are seen to be 29 > 33 > 32 > 31 > 30. The adduct 33 and 29 have some higher value for than expected because of the monodentate linkage of malonate function with the cobalt metal. All the other important IR absorption values of cobalt(II) malonate and their adducts including those derived from Lewis-bases are given in Table 5.8.

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

235

Table 5.8

IR spectral data of cobalt(II) malonate and its various Lewis-base adducts isolated (cm-1)
22 3230 1618 1450 168 1372 29 3395 1557 1327 230 1318 1057 3290 3202 1585 702 573 30 3243 1597 1441 156 1314 1615 1474 754 1019 428 650 31 3240 1598 1440 158 1341 1618 1460 729 421 640 32 3250 1611 1445 166 1316 1625 1489 489 631 33 3390 1578 1350 228 1298 1042 3298 3207 1590 696 480 -

Adducts (O-H) as(CO2) s(CO2) (C-O)

C C C N
(C-N) (C-H) (C-H) (NH2) (NH2) NH2 wag MN stret. Ring deformation (outplane) (inplane)

5.3.7 Electronic spectra and magnetic data of Lewis-base adducts of cobalt(II) malonate The electronic spectra of all the adducts of cobalt(II) malonate were recorded either in solution or in solid state. Some of the spectra are reproduced in Fig.5.2. All the adducts were seen to have the set of bands in the region 15570-15770 and 19880-21730 cm-1. These are

236

Chapter 5

very characteristic of octahedral Co(II) complexes and could be assigned to 4T1g 4A2g and 4T1g 4T1g(P) transitions of the d7 system respectively.(33,34) The data are tabulated in Table 5.9.

Fig. 5.2:

Electronic spectra of cobalt(II) malonate and its Lewis-base adducts : (a) [Co(H2O)2(mal)]n , 22 (b) [(Co(en)2 mal).H2O]n, 29 (c) [Co(bipy)2(H2O)2]mal, 30 d) [Co(phen)2(H2O)2]mal, 31 (e) [Co(py) (H2O)mal]n, 32 f) [(Co(pn)2mal).H2O]n, 33

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

237

Table 5.9: Electronic spectral and magnetic moment data of Lewisbase adducts of cobalt(II) malonate isolated
Adducts Abs. max

(cm-1)

Assignments
4T 1g

eff (BM) 4.53

22

19340 14380

4T1g (P) 4A2g

4T 1g 4T 1g

29

21730 15770 21050 15670 20830 15570

4T1g (P) 4A2g

4T 1g 4T 1g

4.69

30

4T1g (P) 4A2g

4T 1g 4T 1g

4.75

31

4T1g (P) 4A2g

4T 1g 4T 1g

4.79

32

19880 15600 21270 15690

4T1g (P) 4A2g

4T 1g 4T 1g

4.62

33

4T1g (P) 4A2g

4T 1g

4.65

The magnetic moment values for all the adducts were found to be in the range 4.62-4.79 BM. In an octahedral field, the ground state is triply degenerate which would cause an orbital angular momentum contribution to the magnetic moment. The comparatively high value of eff observed (as compared to the spin-only value) for the Co(II) adducts testify the octahedral nature of the complexes. Eventhough there are marginal differences in the magnetic moments observed for the complexes no definite trend in eff values could be seen among these adducts.

238

Chapter 5

All the analytical, spectra (IR, electronic) and magnetic moment data of the adducts of cobalt(II) malonate clearly indicate that all of them have a general octahedral geometry. While the adducts 29 and 33 can be expected to be having a polymeric structure linked monodentatively via malonate carboxylates (with overall octahedral geometry). The pyridine adduct 27 can be considered having a polymeric structure with interlinking bidentatively chelating malonate functions. The high solubility observed for 30 and 31 along with their spectral data, however, suggest that they contain discrete cationic units with ionic malonates. 5.3.8 Interaction of Lewis-bases with polymeric copper(II) malonate Just as in the case of nickel(II) and cobalt(II) malonate, adduct formation studies were investigated with copper(II) malonate also with the same set of Lewis-bases. The interaction was studied in various reaction conditions and also by changing the stoichio metric ratio of the parent malonate and Lewis-bases. The details are presented in Table 5.4. As indicated in the preparative section and also as referred in Table 5.4, the depolymerisation of polymeric parent complex and consequent adduct formation occur with comparative ease with en, pn, bipy and phen at the addition of ligand itself. obtained. 5.3.9 IR spectra of Lewis-base adducts of copper(II) malonate The appearance of several additional and modified peaks in the spectra of the adducts of copper(II) malonate are due to the presence of Lewis-base moiety in them. The important IR The analytical data shown in Table 5.5 confirm the composition of all the adducts

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

239

vibrations

are

presented

in

Table

5.10

along

with

their

assignments.

The as(CO2) band occurring at 1602 cm-1 in 23 in its adducts and the

was found shifted to 1551-1591 cm-1

s(CO2) band occurring at 1370 cm-1 to 1365-1425 cm-1 in them. In the IR spectra of the adducts 34 and 36, the as(CO2) and s(CO2) bands were observed at 1573, 1365 cm-1 (34) and 1591, 1378 cm-1 (36) respectively. The values of these adducts (208 cm-1 for 34 and 213 cm-1 for 36) are characteristic of the monodentate linkage of the carboxylate groups in them.(29,30) However, for the adducts 35, 37 and 39, the as(CO2) and s(CO2) bands were seen at 1578, 1425 cm-1 (35); 1580, 1424 cm-1 (37) and 1551, 1402 cm-1 (39) respectively. The values for these adducts (153 cm-1 for 35, 156 cm-1 for 37 and 149 cm-1 for 39) clearly testify the non-coordinated nature of the carboxylate group in them. But for the adduct 38, the as(CO2) and s(CO2) bands are observed at 1590 and 1420 cm-1 with a value of 170 cm-1 indicating the bidentate linkage of -COO group in them. The order noticed for among the various adducts are found to be 36 > 34 > 38 > 37 > 35 > 39. The value of 34 and 36 are comparatively much higher than that for other adducts. This may be due to the monodentate linkage of malonate moiety with the metal.

240

Chapter 5

Table 5.10 IR spectral data of Lewis-base adducts of copper(II) malonate (cm-1)

Adducts (O-H) as(CO2) s(CO2) (C-O) 23 3230 1602 1370 232 1360 34 1573 1365 208 1328 1056 3297 3244 1626 725 540 35 3410 1578 1425 153 1318 1045 3295 3218 1583 710 723 1029 36 3250 3380 1591 1378 213 1325 1658 1480 37 3390 1580 1424 156 1321 1620 1468 728 38 3240 1590 1420 170 1344 1601 1441 39 3450 1551 1402 149 1327 1028 3330 3260 1630 702 486

C C C N
(C-N) (C-H) (C-H) (NH2) (NH2) NH2wag MN stret Ring deformation (outplane) (inplane)

436 648

425 640

439 698

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

241

5.3.10

Electronic spectra and magnetic data of Lewis-base adducts of copper(II) malonate The electronic spectra of all the adducts of copper(II) malonate

were recorded either in solid state or in solution and are shown in Fig. 5.3. The data are presented in Table 5.11 along with their assignments. In the adducts 35, 37 and 39, broad bands occur in the region 15310-17730 cm-1 assignable to the 2B1g 2A1g transition
B

consistent with a square planar geometry in these adducts.(35-37) Moreover both n * and * bands were found to be blue shifted and appearing in the region 32570-33330 and 40810-41150 cm-1 respectively, compared to that of the parent complex. Broad bands were observed at 15550 cm-1 for the en adduct 34 and at 14920 cm-1 for the py adduct, 38. However, for the bipy adduct, 36, two bands are observed at 11420 cm-1 and 15770 cm-1 which could be tentatively assigned to the d-d transitions 2B1 2A2
B

and 2B12E, respectively of the d9 system with C4v site symmetry.(39)

B

Further, all the adducts exhibit an intense absorption band in the region 25310-27770 cm-1 which could be due to charge transfer transition. The magnetic moment values of the various copper(II) malonate complexes were seen to be in the range 1.69-1.81 BM. The eff value of the py adduct, 38 was found to be lower when compared to the other adducts. This may be due to the possibility of some metal-metal interaction still existing in 38 as in its parent polymeric complex 23. This is quite possible as py cannot possibly break up the polymeric skeleton of 23, because of its comparatively poor ligating power compared to other chelating Lewis-bases.

242

Chapter 5

(a) [Cu(H2O)2mal]n, 23 (b) [Cu(en)2]mal.H2O, 35 (c) [Cu(bipy)(mal)H2O] .H2O, 36 (d) [Cu(phen)2]mal.2H2O, 37 (e) [Cu(py)(H2O)mal]n , 38 (f) [Cu(pn)2]mal.2H2O, 39 (g) [Cu(en)mal], 34

Fig. 5.3: Electronic spectral data of copper(II) malonate and its Lewis-base adducts

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

243

Table 5.11 Electronic spectral and magnetic moment data of Lewisbase adducts of copper(II) malonate
Adducts Absorption max

(cm-1)

Assignments * n* Charge transfer

2B 1g 2A 1g

eff (BM)

40000

23

32360 25120 13670 40983

1.64

* n* Charge transfer
2B 1g 2A 1g

34

32780 25640 15550 41150

1.75

* n* Charge transfer
2B 1g 2A 1g

35

32570 26310 17730 40810

1.81

* n* Charge transfer
2B 1 2E

36

33550 25310 15770 41150 33330 26450 15310 40480 33220 27770 14920 40810 32670 27100 16520

1.77

* n* Charge transfer
2B 1g 2A 1g

37

1.80

* n* Charge transfer
2B 1g 2A 1g

38

1.69

* n* Charge transfer
2B 1g 2A 1g

39

1.79

244

Chapter 5

5.3.11. Crystal and Molecular structure It was possible for us to get quality single crystal of 36 (by carrying out crystallisation in methanol-chloroform mixture) which were good enough for crystal structure analysis. The analysis was carried out using a computer-controlled Semens P4 diffractometer equipped with a graphite monochromatized Mo-K radiation ( = 0.71073/). It shows that the complex 36 crystallizes in the triclinic space group, P-l with a = 7.146 (2) , b = 10.693(2) , c =10.375(3) , =105.75 (3)o, = 105.34(2)o, = 104.56(2)o, V = 689.8(3) , Z = 2, Dc = 1.723g cm-3, R1 = 0.0354, wR2 = 0.0452 (I >2 (I)); R1 = 0.0454, wR2 = 0.0525 (for all data), and S =1.074. Cell parameters were determined by a least squares calculation based on the setting angle and 25 reflections with angles ranging from 1.84 to 24.99o at 293(2)K. A total of 3468 independent reflections was measured. The structure was solved by the direct method (SHELX86 and SHELX93)(40,41) and by the full-matrix least-squares on F2. The largest peak and hole on the final difference-Fourier map had the value of 0.561 and -0.572 e -3, respectively. Selected interatomic distances and bond angles are given in Table 5.12.

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

245

Table 5.12
Cu(1)-O(1) Cu(1)-O(2) Cu(1)-N(2) Cu(1)-N(1) Cu(2)-O(6) Cu(2)-N(3) Cu(2)-O(5) Cu(2)-N(4) 1.886 (9) 1.949(9) 1.932(7) 2.046(9) 1.907(9) 1.985(7) 1.966(8) 2.001(9)

Selected bond lengths () and angles/o

O(1)-Cu(1)-O(2) O(1)-Cu(1)-N(2) O(2)-Cu(1)-N(2) O(1)-Cu(1)-N(1) O(2)-Cu(1)-N(1) N(2)-Cu(1)-N(1) O(6)-Cu(2)-N(3) O(6)-Cu(2)-O(5) 95.8(5) 172..2(5) 89.8(4) 90.8 (4) 169.8 (4) 82.9(4) 172.3(5) 96.2(4) N(3)-Cu(2)-O(5) O(6)-Cu(2)-N(4) N(3)-Cu(2)-N(4) O(5)-Cu(2)-N(4) 86.5 (4) 92.3(4) 84.3(4) 169.4(4)

The ORTEP drawing of the crystal is shown in Fig. 5.4 which shows the favoured coordination polyhedron for the Cu atom. Fig 5.5 shows the coordination environment around Cu in the complex.

246 Fig 5.4 ORTEP drawing of [Cu(bipy)(mal)H2O].H2O, 36

Chapter 5

The

crystal

structure

consists

of

one-dimensional The Cu pyramidal

copper(II) complex resulting from the arrangement of mononuclear mixed ligand copper(II) fragments via hydrogen bonds. atom is five-coordinate in a distorted square

environment. Four of the coordinated atoms are two oxygen atoms of mal moiety and two nitrogen atoms of the bipy ligand with Cu(1)-O(1) =1.886(9) , Cu(1)-O(2) =1.949(9) , Cu(1)-N(1)=2.046(9) , Cu(1)-N(2)=1.932(7) . The O(1), O(2), N(1), N(2) atoms form a plane with the copper(II) ion above the main plane 0.0875 . It is noteworthy that one O atom (OW2), which is in the same side of plane with copper(II) ion, is bonded to Cu with a distance of 2.550 , which can be considered a weak contact. The interaction between Cu1 and O6 is weak, the distance between these two atoms is about 3 . The malonate moiety is seen to be bonded to Cu ion forming a stable 6-membered metallocycle. It is interesting to note that the distorted -CH2- moiety of the coordinated malonate and the coordinated H2O molecule lie in the same direction of the one-dimensional arrangement of each layer and also that the two neighbouring layers have these out-of-plane moieties pointing towards each other, making an almost vacant extended channel. Such an arrangement also provides an opportunity for an appreciable - interaction between bipy moieties of two [Cu(bipy)(mal)H2O] units facing each other (Fig 5.6). The uncoordinated water molecule, OW(4), is hydrogenbonded to the coordinated water molecule, OW(2), with the OW(4) OW(2) contact of 2.811 . In addition, the O atom of the mal ligand (O7) is also hydrogen-bonded to OW(4), with the

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

247

OW(4).O(7) distance of 2.765 . In the light of the division of the strength of hydrogen bonds those with the O.O distance equal to 2.73 or less can be considered strong, whereas those greater than 2.73 are considered weak.(42) Accordingly, the crystallographic results imply that the hydrogen bonds are weak. The asymmetric unit and unit cell of the crystal and crystal packing are shown in Fig 5.5 and Fig 5.6 respectively.

Fig.5.5 Asymmetric unit of the crystal

248

Chapter 5

Fig. 5.6 Unit cell of the crystal showing crystal packing

5.3.12

EPR spectra of Lewis-base adducts of copper(II) malonate.

X-band EPR spectra of parent copper(II) malonate complex, 23 and its adducts were either recorded in solution state (1:1 methanol-toluene mixture) at liquid nitrogen temperature or in solid state. The relevant portions of the spectra of 23 and some of the adducts are presented in Fig 5.7 (i), 5.7 (ii) and also in Fig 5.8. The various spin-Hamltonian parameters were calculated from the spectra using DPPH or TCNE radicals as the g marker. The data are tabulated in Table 5.13. The spectra of 23 taken in solution could be analysed considering the presence of two magnetic species in solution. The relevant hyperfine peaks are indicated in Fig 5.7 (ii). The A values for these two species are seen to be 140 G and 100 G which are comparatively low. We expect that the unique bonding feature of malonate moiety makes it to yield two structural forms for the Cu(II) complex. Considerable spin-delocalisation can

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

249

be expected in both cases as the A values are substantially low. This is also evident from considerable degree of -covalency of metal ligand bond (2Cu = 0.6269) and low value of G, indicative of exchange interaction. The spectra of 35, 36 and 37 in solution at 77K (Fig 5.8) gave well resolved parallel components and unresolved perpendicular components. The hyperfine constant A for these are moderately high at 190 G for 35, 170 G for 36 and 160 G for 37. While 35 is en adduct, 36 and 37 are bipy and phen adducts of copper(II) malonates. The comparatively high A for 35 suggests that the electron spin is more localised in Cu(II) dx2-y2 orbital(43) of en adduct than in bipy and phen adducts. It implies that in bipy adduct 36 and phen adduct 37 there is more spin delocalisation onto the Lewis-base. This is very much expected because en is totally a -donor (with no acceptor property) while bipy and phen can be considered as -donor as well as -acceptors because of their low-lying * orbitals. The tricyclic phen has better -acceptor property than the bicyclic bipy. Because of this, electron spin gets delocalised more on phen adduct 37 than in bipy adduct 36. Compared to en adduct 35 which has A = 190 G, the pn adduct 39 has its A = 180 G. Correspondingly 2Cu for 35 and 39 are 0.8072 and 0.7939 respectively. Commensurate with this spindelocalisation trend is the Cu-N -covalency order. The overall trend in 2Cu values
)

indicate

that

the

covalency

order

is

37 > 36 > 39 > 35 quite in agreement with the extent of electron spin-delocalisation.(44,45 The G value of the adducts 34, 35, 36, 37 and 39 indicate that no considerable exchange interaction possible for these adducts (G > 4). However, in the case of the adduct 38, we expect appreciable exchange interaction because of its low G value (G < 4).

250

Chapter 5

(i) Fig.5.7

(ii)

EPR spectra of copper(II) malonate and its adducts: (a) [Cu(H2O)2mal]n, 23, in solution at 300 K (b) [Cu(en)mal], 34 (solid state, 77 K) and (c) [Cu(py)(H2O)mal]n, 38 (solid state, 300 K); Expanded version of (a) is given separately

Fig. 5.8

EPR spectra of various adducts of copper(II) malonate in solution (1:1 toluene-methanol mixture) at 77 K (a) [Cu(en)2]mal.H2O, 35 (b) [Cu(bipy)(mal)H2O].H2O, 36

(c) Cu(phen)2]mal.2H2O, 37

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

251

Table 5.1.3

EPR parameters of copper(II) malonate and its various Lewis-base adducts A (gauss)
(I) (II) 140 100 190

Compound

A (gauss)
46.66 46.66 53.33 66.66

g
2.18 2.16 2.17 2.23

g
2.05 2.05 2.04 2.03

giso 2.09 2.09 2.08 2.10

2Cu 0.6269 0.4958 0.8072

G 3.6 3.2 4.25 7.67

[Cu(H2O)2mal]n
23

[Cu(en)mal] 34 [Cu(en)2]mal.H2O 35 [Cu(bipy) (mal)H2O].H2O 36 [Cu(phen)2] mal.2H2O 37 [Cu(py)(H2O)mal]n 38 [Cu(pn)2]mal.2H2O 39

170

56.66

2.26

2.04

2.11

0.7861

6.50

160

60

2.27

2.04

2.12

0.7683

6.75

180

50 60

2.17 2.24

2.10 2.04

2.12 2.11

0.7939

1.7 6.0

The chemical composition, IR, electronic and EPR spectral data along with magnetic values indicate that the adducts 35, 37 and 39 possess a more or less planar structure containing ionic malonate. However, the adduct 34 can be expected to be having a four coordinate planar structure linked monodentatively via malonate carboxylates similarly the adduct 38 can be considered having an overall octahedral (distorted) structure and polymeric in nature with interlinking bidentatively chelating malonate functions. The spectral data of 36 are in conformity with the crystal structure data revealing its square-pyramidal structure.

252

Chapter 5

References: 1. (a) A. Michaelides, V. Kiritsis, S. Skoulika and A. Aubry, Angew. Chem. Int. Ed; 105 (1993) 1525 (b) A. Michaelides, V. Kiritsis, S. Skoulika and A. Aubry, Angew. Chem. Int. Ed; 32 (1993) 1495 (c) B. Benmerad, A. G. Laidoudi, F. Balegroune and H. Birkedal, Acta Crystallogr; C56 (2000) 789 (d) J. Perles, M. Iglesias, C. R. Valero and N. Snejko, Chem. Commun; (2003) 346 (e) A. Michaelides, S. Skoulika, V. Kiritsis and A. Aubry, J. Chem. Soc. Chem. Commun; (1995) 1415 2. (a) A. Dimos, D. Tsaousis, A. Michaelides, S. Skoulika, S. Golhen, L. Ouahab, C. Didierjean and A. Aubry, Chem. Mater; 14 (2002) 2616 (b) B. Q. Ma, D. S. Zhang, S. Gao and G. X. Xu, Angew. Chem. Int. Ed; 112 (2000) 3790 (c) B. Q. Ma, D. S. Zhang, S. Gao and G. X. Xu, Angew. Chem. Int. Ed; 39 (2000) 3644 (d) R. Baggio, M. T. Garland, M. Perec and D. Vega, Inorg. Chem; 35 (1996) 2396 (e) A. C. Razzi, R. Calvo, R. Baggio, M. T. Garland and O. Pena, Inorg. Chem; 41 (2002) 5609 3. (a) M. Eddaoudi, D. B. Moler, H. Li, B. Chen, T. M. Reineke, M. O Keeffe and O. M. Yaghi, Acc. Chem. Res; 34 (2001) 319 (b) M. Eddaoudi, J. Kim, D. Vodak, A. Sudik, J. Wachter, M. O Keeffe and Yaghi, Proc. Natl. Acad. Sci. USA; 99 (2002) 4900 (c) H. Li, M. Eddaoudi, M. O Keeffe and O. M. Yaghi, Nature; 402 (1999) 276

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

253

(d) O. M. Yaghi, Metal Containing Polymeric Materials, Plenum, New York, (1996), p. 219 (e) O. M. Yaghi, Modular Chemistry, Kluwer, Boston, (1997) p. 663 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. B. Benmerad, A. G. Laidoudi, G. Bernardinelli, F. Balegroune. Acta Cryst.C56 (2000) 321. P. Barbaro, F. Cecconi, C. A. Ghilardi, L. Alderighi, E. Chinea and A. Mederos, Inorg. Chim. Acta; 252 (1997) 187 L. Lezama, J. L. Pizarro and T. Rojo, Euro. J. Inorg. Chem; (1999) 935 C. R. Perez, M. H. Molina, J. Sanchiz and T. Lopez, Inorg. Chim. Acta; 298 (2000) 245 R. Vaidhyanathan, S. Natarajan and C. N. R. Rao, J. Chem. Soc. Dalton Trans; (2003) 1459 C. R. Perez, M. H. Molina, J. Sanchiz and T.Lopez, Inorg. Chim. Acta; 298 (2000) 202 Y. R. Martin, C. R. Perez, J. Sanchiz and M. Julve, Inorg. Chim. Acta; 318 (2001) 159 B. J. Bae and I. H. Suh, J. Organomet. Chem; 648 (2002) 214 C. R. Perez, J. Sanchiz, M. H. Molina, F. Lloret and M. Julve, Inorg. Chem; 39 (2000) 1363 C. R. Perez, J. Sanchiz, M. H. Molina, F. Lloret, J. Cano and M. Julve, Inorg. Chem; 39 (2000) 3845 E. V. Brusau, G. E. Narda, J. C. Pedregosa and G. M. Punte, J. Solid State. Chem; 143 (1999) 174 I. G. Filippova, V. K. Kravtsov and M. Gdanec, Russ .J. Coord. Chem; 26 (2000) 809

254

Chapter 5

16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28.

Y. R. Martin, C. R. Perez, J. Sanchiz and M. Julve, Inorg. Chim. Acta; 326 (2001) 20 H. Y. Shen, W. M. Bu, D. Z. Liao, Z. H. Jiang and S. P. Yan, Inorg. Chem. Commun; 3 (2000) 497 L. Alderight, F. Cecconi, C. A Ghilardi, A. Mederos and A. Vacca, Polyhedron; 18 (1999) 3305 F. S. Delgado, J. Sanchiz, C. R. Perez, F. Lloret and M. Julve, Inorg. Chem; 42 (2003) 5938 X. Wenmei, W. Qiguang, Y. Lan and Y. Rudong, Polyhedron; 11 (1992) 2051 F. Marrot and J. C. Trombe, Polyhedron; 13 (1994) 1931 Y. Zhang, J. Li, J. Chen, Q. Su and W. Deng, Inorg. Chem; 39 (2000) 2330 A. Cuevas, R. Chiozzone, C. Kremer, L. Suescun, A. Mombru, J. Cano, F. Lloret and J. Faus, Inorg. Chem; 43 (2004) 7823 D. Pasini, P. P. Righetti and V. Rossi, Org. Lett; 4 (2002) 23 D. Necas, M. Tursky and M. Kotora, J. Am. Chem. Soc; 126 (2004) 10222 G.B. Deacon and R. Philips, Coord. Chem. Rev; 88 (1980) 227 L. P. Battaglia, A. B. Corradi, G. Marcotrigiano. L. Menabue and G. C. Pellacani, J. Am. Chem. Soc; 102 (1980) 2663 L. Antolini, L. P. Battaglia, A. B. Corradi, G. Marcotrigiano, L. Menabue, G. C. Pellacani and M. Saladini, Inorg. Chem; 21 (1982) 1391 K. Nakamoto, Infrared & Raman Spectroscopy of Inorganic and Coordination compounds. Wiley, New York , (1978) A. Braibanti, F. Dallavalle, M. A. Pellinghelli and E. Leporati, Inorg. Chem; 7 (1968) 1430

29. 30.

Interaction of Lewis-bases with Polymeric Metal(II) Malonates

255

31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45.

R. S. Drago, Physical Methods in Chemistry Saunders, Philadelphia (1969) A. B. P. Lever Inorganic Electronic Spectroscopy. 2nd Ed, Elsevier, Amsterdam, (1984) A. B. P. Lever, Inorganic Electronic Spectroscopy 2nd Ed, Elsevier, Amsterdam, (1968) 534 K. Dey and D. Padhayay, Indian. J. Chem; 31A (1992) 34 R. H. Holm and M. J. O Connor, Prog. Inorg. Chem; 14 (1971) 241 F. A. Cotton and J. J. Wise, Inorg. Chem; 6 (1967) 917 G. Marcotrigiano, L. Menabue, G. C. Pellacani and M. Saladini, Inorg. Chim. Acta; 34 (1979) 43 B. Konig Structure and Bonding Springer- Verley, Berlin, Vol.9, (1979) A. A. G. Tomlinson and B. J. Hathaway, J. Chem. Soc. A (1968) 1905 SPD-PLUS, Enraf-Nonius, Delft, The Netherlands, (1985) G. M. Sheldrick, Acta Crystallogr; Sect. A; 46 (1990) 467 I. D. Brown, Acta Crystallogr; Sect. A; 32 (1976) 24 B. Singh, B. P. Yadava and R.C. Aggarwal, Indian. J. Chem; 23A (1984) 441 R. Neiman and D. Kivelson, J. Chem. Phy; 35 (1961) 149 J. Peisach and W. E. Blumberg, Arch. Biochem. Biophy; 165 (1974) 691

Chapter 6 Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) and their Lewis-base Adducts

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

257

6.1

Introduction
e have seen in the case of various adducts of metal succinate that the nature of thermal dissociation depends on the type of metal, the mode of coordination

of the succinate moiety and also on the type of Lewis-bases involved. Eventhough one can consider the two carboxylate moieties of the malonate as isolated groups as in succinate, because of the intervening CH2- linker, we could see that the

malonate dianion can coordinate to the metal in an unique manner besides their usual ligation modes. In its special coordinate mode, the dianionic malonate not only chelates strongly (forming a 6membered ring) but also charge compensates the dicationic metal ion. Consequently one can expect a substantial change in the ligation of Lewis-bases and also their dissociation on thermal activation. The rates of ligand substitution reactions involving Ni(II) and malonate anions have been reported earlier.(1-3) The thermal decomposition of [Mn(mal)(H2O)2](4), shows a two step process both involving a three-dimensional diffusion mechanism. Complexes of the type [SrM(mal)2(H2O)5].2H2O(5) (M = Mn, Fe, Co and Ni] also exhibit such three step thermal process involving dehydration, ligand pyrolysis followed by inorganic residue formation. Mohamed et al(6,7) reported that [M(mal)(H2O)2] (M = Co(II), Ni(II)), decompose in two steps in both N2 and air. Report is also available on the decomposition features of chromium(III) complexes of substituted malonates with composition K3[Cr(L)3].3H2O(8) (L = malonate, monomethyl malonate, dimethyl malonate). Some mention is also made about the thermal

258

Chapter 6

behaviour of Cu(II) and Zn(II) malonates in an atmosphere of static air and dry N2.(9) Complexes of the type (N2H5)2[M(mal)2(H2O)2](10) (M = Co, Ni or Zn), are seen to undergo exothermic reaction. An overview of these reports shows that no systematic study have been reported for metal malonates and their various Lewis-base adducts. In the present chapter, we discuss in detail the thermal dissociation features of the adducts of metal malonates and present various thermodynamic parameters associated with the decomposition stages.

6.2

Results and Discussion

The thermal decomposition characteristics of six coordinated

complexes of Ni(II), Co(II) and four coordinated complex of Cu(II) along with their four coordinated and six coordinated Lewis-base adducts were studied in nitrogen atmosphere, with a heating rate of 100C min-1. The phenomenological aspects, kinetic and thermodynamic parameters associated with the thermal reactions and the trend in thermal behaviour of various adducts of metal malonates are discussed below.

6.2.1 Phenomenological Aspects

6.2.1.1 Thermal decomposition of nickel(II) malonate in N2 The thermogram of [Ni(mal)(H2O)]n in nitrogen atmosphere given in Fig 6.1 shows a two stage thermal decomposition.(6,7) This compound is found to be thermally stable only upto 1900C. The decomposition of the complex is seen starting at 1900C (Ti) and progressing till 2750C (Tf) with a peak temperature of 256.800C (Ts). The weight loss corresponding to this decomposition stage amounts to 18.39%. From the elemental analysis and spectroscopic methods it

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

259

was found that the ligand (mal)2- gets coordinated to the metal ion through its oxygen atoms. During heating in the first step, the loss of two coordinated water takes place. The mass loss observed (18.39%) for this decomposition stage was in good agreement with the theoretical value of 18.30%. The second stage of decomposition is seen starting immediately after the first at 2750C (Ti) and ending at 3570C (Tf) with a peak temperature of 352.900C (Ts). This could be attributed to the decomposition of [Ni(mal)]n to NiO. The loss in mass corresponding to this decomposition stage was 44.15%, which is also in good agreement with the theoretical value of 43.73%. The mass of the residue observed after the decomposition was 37.46% which is in close agreement with the theoretical value of 37.97%. The authenticity of the final product, NiO, was also confirmed by elemental analysis.

Fig. 6.1 The thermogram (TG/DTG) of [Ni(H2O2)mal]n in N2

The decomposition features are summarised below in Table 6.1. [Ni(H2O)2mal]n

, N2 o 190 - 275 C

[Ni(mal)]n + 2H2O

... (6.1)

[Ni(mal)]n

, N2 275 - 357 oC

NiO + gaseous products .. (6.2)

260

Chapter 6

Table 6.1 Thermal characteristics of [Ni(mal)(H2O)2]n

Compound Temp range (0C) 190-275 [Ni(mal)(H2O)2]n 275-357 Above 357 Peak temp (0C) 256.80 352.90 Wt. loss (in%) Stages I II Found 18.39 44.15 37.46 Calcd 18.30 43.73 37.97 Probable reaction eq. 6.1 eq. 6.2 NiO

6.2.1.2 Lewis-base adducts of nickel(II) malonate (a) [Ni(en)2(H2O)2]mal, 24 From the thermogram given in Fig 6.2, it is observed that this compound is thermally stable only upto 800C. The first stage decomposition is seen starting at 800C (Ti) and progressing till 1280C (Tf) with a peak temperature (Ts) of 1200C. The weight loss during this stage amounts to 11.49%. This could be attributed to the loss of two moles of coordinated water from the adduct. The mass loss calculated (11.37%) for this stage agrees well with the observed value. A well defined horizontal region after the first stage of decomposition in the range 128-1750C supports the formation and the stability of [Ni(en)2]mal. The authenticity of the product after the first stage decomposition is also confirmed by spectroscopic analysis of the product at this stage.

Fig. 6.2 The thermogram (TG/DTG) of [Ni(en)2(H2O)2]mal in N2.

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

261

The second stage of decomposition was seen in the range 175-2600C. During the stage the mass loss observed was 19.48%. This could be due to the loss of 1 mole of en from the adduct. The mass loss calculated (18.95%) agrees well with the observed value of 19.28%. The third stage of decomposition starts immediately after the second at 2600C and progresses upto 3100C. The mass loss observed in this stage was 46.16% which is in perfect match with the calculated value of 46.10%. In this stage the loss of one mole en together with the decomposition of malonate moiety can be expected to takes place to yield NiO as the final product. The residual percentage of 23.07% observed, is in good agreement with the theoretical value of 23.58%. The decomposition features are summarised below and in Table 6.2. [Ni(en)2(H2O)2]mal

, N2 o 80 - 128 C

[Ni(en)2]mal + 2H2O.. (6.3)

[Ni(en)2]mal

[Ni(en)mal]n + en 175 - 260oC

, N2

... (6.4)

[Ni(en)mal]n

, N2 260 - 310 oC

NiO + en + gaseous products. .... (6.5)

Table 6.2. Thermal characteristics of [Ni(en)2(H2O)2]mal

Compound Temp range (0C) 80-128 . [Ni(en)2(H2O)2]mal 175-260 260-310 Above 310 Peak temp (0C) 120.00 251.60 285.80 Wt. loss (in%) Stages I II III Found 11.49 19.28 46.16 23.07 (residue) Calcd 11.37 18.95 46.10 23.58 (residue) Probable reaction eq. 6.3 eq. 6.4 eq. 6.5 NiO

262

Chapter 6

(b)

[Ni(bipy)2(H2O)2]mal, 25 The thermogram of the adduct is given in Fig 6.3. The initial

decomposition of this compound is seen starting at 900C and progressing till 1200C. The weight loss corresponding to this decomposition stage amounts to 7.33% which is in close agreement with the calculated value of 7.07% for the loss of two moles of coordinated water. The second stage of decomposition commences at 2900C and ends at 3100C with a high mass loss. During this stage the loss of two moles of bipy moieties together with the decomposition of malonate moieties can be expected to takes place to yield NiO as the final product. The loss in mass corresponding to this decomposition stage is found to be 78.42% with the mass of the residue being 14.25%. After 3100C, the compound is seen stable in the N2 atmosphere. summarised in Table 6.3. Some of the thermal features are

Fig. 6.3. Thermogram (TG/DTG) of. [Ni(bipy)2(H2O)2]mal in N2

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

263

The decomposition features are summarized below. [Ni(bipy)2(H2O)2]mal [Ni(bipy)2]mal + 2 H2O. (6.6) 90- 120o C

, N2

[Ni(bipy)2]mal

o NiO+2 bipy + gaseous products.. (6.7) 290 - 310 C

, N2

Table 6.3 Thermal characteristics of [Ni(bipy)2(H2O)2]mal

Temp range (0C) 90-120 [Ni(bipy)2(H2O)2]mal 290-310 Above 310 Peak temp (0C) 117.60 291.80 Wt. loss (in%) Stages I II Found 7.33 78.42 14.25 (residue) Calcd 7.07 78.25 14.67 (residue) Probable reaction eq. 6.6 eq. 6.7 NiO

Compound

(c)

[Ni(phen)2mal].3H2O, 26 The thermogram of this adduct is shown in Fig. 6.4. The

thermal decomposition of this compound is seen starting at 500C and ending at 800C, with a Ts of 550C. The loss in mass corresponding to this decomposition amounts to 8.94% is in close agreement with the theoretical value of 8.84% for the loss of three moles of lattice water. A well defined horizontal region after the first stage of decomposition in the range 80-3100C supports the stability of [Ni(phen)2mal]. The second stage of decomposition is seen starting only at 3100C and ending at 4800C. In this stage the loss of 2 moles of phen moieties together with the decomposition of malonate moiety can be expected to take place to yield NiO as the final product. The mass loss corresponding to this stage is observed to be 79.10% which is in close match with the theoretical value of 78.94%. The mass of the residue after the complete

264

Chapter 6

decomposition was found to be 11.96%. The decomposition features are summarised below and tabulated in Table 6.4.

Fig. 6.4. The thermogram (TG/DTG) of [Ni(phen)2mal].3H2O

The decomposition features are summarized below

[Ni(phen)2mal].3H2O

, N2 o 50 - 80 C

[Ni(phen)2mal] + 3H2O ...(6.8)

[Ni(phen)2mal]

, N2 310 - 480 oC

NiO + 2 phen+gaseous products ...

(6.9) Table 6.4. Thermal characteristics of [Ni(phen)2mal].3H2O

Compound [Ni(phen)2mal]. 3H2O Temp range (0C) 50-80 310-480 Peak temp (0C) 55 339 Wt. loss (in%) Stages I II Found 8.94 79.10 Calcd 8.84 78.94 Probable reaction eq. 6.8 eq 6.9

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

265

Above 480

11.96 (residue)

12.22 (residue)

NiO

(d)

[Ni(pn)2(H2O)2]mal.2H2O, 28 The thermogram of this adduct is shown in Fig.6.5. The

compound is found to be stable only upto 650C. The decomposition is seen starting at 650C (Ti) and progressing till 1000C (Tf). The weight loss corresponding to this stage amounts to 9.20% for the loss of two moles of lattice water. The second stage of decomposition is seen starting at 1000C (Ti) and ending at 1900C (Tf). The weight loss corresponding to this stage amounts to 9.15% which is in close agreement with the calculated value of 9.45% for the loss of two moles of coordinated water. The third stage of decomposition is seen commencing immediately at 1900C (Ti) and progressing till 2000C (Tf) with a mass loss of 19.30%. In this stage the loss of one mole of pn takes place. The fourth stage of decomposition is seen starting at 2000C (Ti) and ending at 3950C (Tf) with a mass loss of 42.23%. During this stage the loss of 1 mole of pn together with the decomposition of malonate moiety can be expected to take place to yield NiO as the final product. The mass loss observed (42.23%) which is in close agreement with the theoretical value of 42.04%. However, the residual mass after the complete thermal process was 20.12% is in good agreement with the calculated value of 19.60% for the formation of NiO. The decomposition features are summarised below and tabulated in Table 6.5.

266

Chapter 6

Fig. 6.5 Thermogram (TG/DTG) of [Ni(pn)2(H2O)2]mal. 2H2O

The decomposition features are summarized below [Ni(pn)2(H2O)2]mal.2H2O

, N2 0

[Ni(pn)2(H2O)2]mal +2H2O ....(6.10)

65-100 C
, N2 0

[Ni(pn)2(H2O)2]mal

[Ni(pn)2]mal +2H2O

... (6.11)

100 - 190 C
[Ni(pn)2]mal
, N2 0

[Ni(pn)mal]n + pn...... (6.12)

190 - 200 C
, N2 0

[Ni(pn)mal]n

NiO + pn + gaseous products .(6.13)

200-395 C

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

267

Table 6.5. Thermal characteristics of [Ni(pn)2(H2O)2]mal.2H2O

Temp range (0C) 65-100 [Ni(pn)2(H2O)2]mal. 2H2O 100-185 185-200 200-395 Above 3950C Peak temp (0C) 84 169 196 310 Wt. loss (in%) Stages I II III IV Found 9.20 9.15 19.30 42.23 20.12 (residue) Calcd 9.45 9.45 19.46 42.04 19.60 (residue) Probable reaction eq. 6.10 eq. 6.11 eq 6.12 eq 6.13 NiO

Compound

6.2.1.3. Thermal decomposition of cobalt(II) malonate in N2 The thermogram of cobalt(II) malonate in nitrogen atmosphere given in Fig.6.6 shows a two stage thermal decomposition.(6,7) This compound is thermally stable upto 1600C indicated by a well defined plateau. The first stage decomposition is seen starting at 1600C (Ti) and progressing till 2300C (Tf) with a peak temperature (Ts) of 2200C. The weight loss during this stage amounts to 18.10% which is in close match with the theoretical value of 18.28% for the loss of two moles of coordinated water. The second stage of decomposition commences only at 2700C and ends at 4350C with a high mass loss. The loss in mass corresponding to this decomposition is 43.55% with the mass of the residue being 38.35%. This could be attributed to the decomposition of [Co(mal)]n to CoO. The residual mass of 38.35% observed in the thermogram is in close agreement with the calculated value of 38.05% for the formation of CoO. After 4350C, the compound is seen stable in the N2 atmosphere. Some of the thermal features are summarised in Table 6.6.

268

Chapter 6

Fig 6.6 The thermogram (TG/DTG) of [Co(H2O)2mal]n in N2

The decomposition pattern could be summarised below

[Co(mal)(H2O2)]n

, N2 160 - 230 oC , N2

[Co(mal)]n + 2H2O . (6.14)

[Co(mal)]n

270 - 435 oC

CoO + gaseous products.. (6.15)

Table 6.6 Thermal Characteristics of [Co(H2O)2mal]n

Temp range (0C) Peak temp (0C) Wt. loss (in%) Stages Found I II 18.10 43.55 38.35 (residue) Calcd 18.28 43.67 38.05 (residue) Probable reaction eq 6.14 eq 6.15 CoO

Compound

160-230 [Co(H2O)2mal]n 270-435 Above 435

220 348 -

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

269

6.2.1.4 (a)

Lewis-base adducts of cobalt(II) malonate

[(Co(en)2mal).H2O]n, 29 The thermogram of the adduct is given in Fig. 6.7. This

compound is found to be stable only up to 500C. The initial decomposition is seen starting at 500C (Ti) and progressing till 1000C (Tf) with a peak temperature of 980C (Ts). The weight loss observed during this stage (6.23%) agrees well with the calculated value of 6.02%. In this stage the loss of one mole of lattice water takes place. During the second stage of decomposition of the adduct (220-2800C), the breaking of the Co(II)-ethylenediamine N bond and the escape of en moiety from the complex takes place. The mass loss observed during this stage is observed to be 49.80%. The third stage of decomposition is seen commencing immediately at 2800C (Ti) and ending at 3500C with a mass loss of 18.53%. The theoretically expected mass loss for this stage is 28.77% which does not agree with the experimental value (18.53%) for the decomposition of malonate moiety to yield CoO and some gaseous products. This is because, the third stage is getting initiated before completing the second stage of decomposition. The mass of the residue after the complete decomposition was found to be 25.44% which is in perfect agreement with the theoretical value of 25.07% for the formation of CoO. Above 3500C, the residue is found to be stable under N2 atmosphere. The decomposition features are given below and tabulated in Table 6.7

270

Chapter 6

Fig. 6.7 The thermogram (TG/DTG) of [(Co(en)2mal).H2O]n in N2

[(Co(en)2mal).H2O]n

, N2

o 50-100 C
, N2

[Co(en)2mal]n + H2O... (6.16)

[Co(en)2mal]n

o 220-280 C
, N2

[Co(mal)]n + 2en

.. (6.17)

[Co(mal)]n

o 280-350 C

CoO + gaseous products . (6.18)

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

271

Table 6.7 Thermal characteristics of [(Co(en)2mal).H2O]n

Compound Temp range (0C) 50-100 220-280 [(Co(en)2mal).H2O]n 280-350 Above 350 Peak temp (0C) 98 265 348 Wt. loss (in%) Stages Found 6.23 49.80 18.53 25.44 (residue) Calcd 6.02 40.14 28.77 25.07 (residue) Probable reaction eq 6.16 eq 6.17 eq 6.18 CoO

I II III -

(b)

[Co(bipy)2(H2O)2]mal, 30 From the thermogram given in Fig 6.8, it is observed that

this compound is thermally stable only upto 800C indicated by well-defined plateau. The first stage decomposition is seen starting at 800C (Ti) and progressing till 1200C (Tf) with a peak temperature (Ts) of 1170C. The weight loss during this stage amounts to 6.88% is in good agreement with the calculated value of 7.07%. In this stage the loss of two moles of coordinated water takes place. A well defined horizontal region after the first stage decomposition in the range 120-2300C supports the stability of [Co(bipy)2]mal. The authenticity of the product after the first stage decomposition is also confirmed by spectroscopic analysis of the product at this stage. The second stage of decomposition of the adduct is due to the breaking of the Co(II)-pyridyl N bond and the loss of bipy moieties from the complex, leaving back the parent complex. During the second stage (2302800C), the mass loss was observed to be 66.58%. The third stage of decomposition is seen commencing immediately at 2800C and ending at 3300C with a mass loss of 11.59% which does not agree with the theoretical value of 16.88% for the decomposition of malonate moiety

272

Chapter 6

to yield CoO and some gaseous products. The residual mass of 14.95% is in good agreement with the theoretical value of 14.72% for the formation of CoO. The decomposition features are summarised below and tabulated in Table 6.8.

Fig. 6.8 The thermogram (TG/DTG) of [Co(bipy)2(H2O)2]mal in N2

[Co(bipy)2(H2O)2]mal

, N2 o 80 - 120 C
, N2

[Co(bipy)2]mal + 2H2O- (6.19)

[Co(bipy)2]mal

[Co(mal)]n + 2 bipy (6.20) 230 - 280o C

[Co(mal)]n

, N2 oC 280 - 330

CoO + gaseous products . (6.21)

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

273

Table 6.8 Thermal characteristics of [Co(bipy)2(H2O)2]mal

Temp range (0C) 80-120 [Co(bipy)2(H2O)2]mal 230-280 280-330 Above 330 Peak temp (0C) 117 278 325 Wt. loss (in%) Stages Found I II III 6.88 66.58 11.59 14.95 (residue) Calcd 7.07 61.33 16.88 14.72 (residue) Probable reaction eq 6.19 eq 6.20 eq 6.21 CoO

Compound

(c)

[Co(phen)2(H2O)2]mal, 31 The thermogram of the adduct is given in Fig 6.9. This

compound is found to be stable only upto 800C. The compound is seen decomposing in three stages with the first one starting at 800C (Ti) and progressing till 1200C (Tf). The weight loss corresponding to this stage amounts to 6.10% which is in close agreement with the theoretical value of 6.07% for the loss of 2 moles of coordinated water. A well defined horizontal region after the first stage decomposition in the range 120-2750C supports the stability of [Co(phen)2]mal. The authenticity of the product after the first stage decomposition is also confirmed by spectroscopic analysis of the product at this stage. The second stage of decomposition is seen starting at 2750C and ending at 8000C with a peak temperature (Ts) of 3050C. The mass loss observed (80.94%) is in good agreement with the theoretical value of 81.30% for the loss of two moles of phen moiety together with the decomposition of malonate moiety can be expected to take place to yield CoO as the final product and some gaseous products. The residual mass of 12.96% agrees well with the

274

Chapter 6

theoretical value of 12.63% for the formation of CoO. The decomposition features are summarised below and tabulated in Table 6.9.

Fig 6.9 The thermogram (TG/DTG) of [Co(phen)2(H2O)2]mal.2H2O in N2

[Co(phen)2(H2O)2]mal

, N2 o 80 - 120 C , N2

[Co(phen)2]mal + 2H2O . (6.22)

[Co(phen)2]mal

CoO + 2phen+ gaseous products. (6.23)

275 - 800 oC
Table 6.9 Thermal characteristics of [Co(phen)2(H2O)2]mal
Compound Temp range (0C) 80-120 [Co(phen)2(H2O)2]mal 275-800 Above 800 Peak temp (0C) 118 302 Wt. loss (in%) Stages Found 6.10 80.94 12.96 Calcd 6.07 81.30 12.63 Probable reaction eq 6.22 eq 6.23 CoO

I II -

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

275

(d)

[Co(py)(H2O)mal]n, 32 From the thermogram (Fig 6.10) it was found that this

compound is seen stable upto 1450C. The mass loss observed in the first stage of decomposition in the temperature range 145-2700C amounts to 37.50%. This could be attributed to the breaking of M-O bond (water) and M-N bond (pyridine) which helps to the escape of one mole of coordinated water along with pyridine moiety, giving back [Co(mal)]n. The loss in mass calculated (37.64%) agrees well with the observed value of 37.50%.

Fig 6.10. The thermogram (TG/DTG) of [Co(H2O)(py)(mal)]n in N2

The second stage is seen initiating immediately after the first stage at 2700C and progressing till 3150C with a mass loss of about 33.15% leaving a residual mass of 29.35%. This stage is due to the thermal decomposition of [Co(mal)]n to CoO and some gaseous products. The residual mass after the complete thermal process was 29.35% which is in perfect agreement with the theoretical value of 29.03%, expected for CoO. The decomposition pattern is summarised below and tabulated in Table 6.10.

276

Chapter 6

[Co(H2O)(py)(mal)]n

, N2 145 - 270 oC

[Co(mal)]n + H2O + py. (6.24)

[Co(mal)]n

, N2 270 - 315 oC

CoO + gaseous products

... (6.25)

Table 6.10 Thermal characteristics of [Co(H2O)(py)(mal)]n

Temp range (0C) Peak temp (0C) 220 305 Wt. loss (in%) Stages Found I II 37.50 33.15 29.35 (residue) Calcd 37.64 33.33 29.03 (residue) Probable reaction eq. 6.24 eq. 6.25 CoO

Compound

145-270 [Co(H2O)(py)(mal)]n 270-315 Above 315

6.2.1.5

Thermal decomposition of copper(II) malonate in N2 given in Fig 6.11

The thermogram of copper(II) malonate

shows a two stage thermal decomposition.(9) The initial decomposition of the compound is seen starting at 2300C and progressing till 2850C. The second stage of decomposition is commencing at 2850C and ending at 3480C with a high mass loss. After 3480C, the compound is seen stable in the N2 atmosphere. Some of the thermal features are summarised in Table 6.11.

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

277

Fig. 6.11 Thermal decomposition of [Cu(H2O)2mal]n in N2

Table 6.11 Thermal characteristics of [Cu(H2O)2(mal)]n

Temp range (0C) 230-285 [Cu(H2O)2(mal)]n 285-348 Above 348 Peak temp (0C) 280 315 Wt. loss (in%) Stages Found I II 17.72 42.54 39.74 (residue) Calcd 17.86 42.67 39.47 (residue) Probable reaction eq.6.26 eq 6.27 CuO

Compound

In the first stage of decomposition the loss of two moles of coordinated water takes place from the complex yielding [Cu(mal)]n. The weight loss corresponding to this decomposition amounts to 17.72% which is agreeing well with the calculated value (17.86%). The second stage is attributed to the decomposition of [Cu(mal)]n to CuO and gaseous products. The mass loss observed during this stage was found to be 42.54% which perfectly matches with the theoretical value of 42.67%. The residual mass after the complete decomposition was observed to be 39.74% which is in good

278

Chapter 6

agreement with the theoretical value of 39.47% expected for CuO. The decomposition features could be summarized below. [Cu(H2O)2(mal)]n

, N2 230 - 285 oC
, N2

[Cu(mal)]n + 2H2O

...(6.26)

[Cu(mal)]n

285 - 348 oC

CuO + gaseous products

... (6.27)

6.2.1.6 Lewis-base adducts of copper(II) malonate (a) [Cu(en)mal], 34 The thermogram of this compound is shown in Fig.6.12. The compound is found to be thermally stable upto 2450C and it has only one decomposition stage. The decomposition is seen starting at 2450C and ending at 3150C, with a Ts of 2700C. The mass loss observed to be 64.64% is in good agreement with the calculated value of 64.73%. The loss in mass could be attributed to the cleavage of bonds between metal ion and ethylenic N which would make the en moiety escape together with the decomposition of malonate moiety to yield CuO as the final product. The residual mass of 35.36% expected for CuO is perfectly match with the theoretical value of 35.27%. The decomposition features is given below and are tabulated in Table 6.12.

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

279

Fig. 6.12. The thermogram (TG/DTG) of [Cu(en)mal] in N2

[Cu(en)mal]

, N2 245 - 315 oC

CuO+ en+ gaseous products .(6.28)

Table 6.12 Thermal characteristics of [Cu(en)mal]

Temp range (0C) 245-315 [Cu(en)mal] Above 315 Peak temp (0C) 270 Wt. loss (in%) Stages Found I 64.64 35.36 (residue) Calcd 64.73 35.27 (residue) Probable reaction eq.6.28 CuO

Compound

(b)

[Cu(en)2]mal.H2O, 35 The thermogram of this compound (Fig.6.13) shows an initial

decomposition starting at 650C (Ti) and ending at 1000C (Tf) with a loss in mass of about 5.86%. In this stage the loss of one mole of lattice water takes place. Both the calculated and theoretical values agreeing well with this (Table 6.13). The second stage of decomposition is seen initiating at 1850C and progressing upto 2150C with a loss in mass of about 19.50%. Because of the volatile

280

Chapter 6

nature of en, the loss of two en moles are expected on heating from the adduct. But for the loss of two moles of en the mass loss calculated was 38.52%, whereas the mass loss found (Stage II) was only 19.50%. This may be due to the loss of one mole of en from the adduct. The weight loss calculated for the loss of one mole en is 19.76% which is agreeing with the observed value of 19.50%.

Fig 6.13 The thermogram (TG/DTG) of [Cu(en)2]mal.2H2O in N2

The

third

stage

of

decomposition

is

seen

initiating

immediately at 2150C and ending at 3500C. During the third stage, the decomposition of an intermediate takes place with the loss of the other molecule of en and breaking of the parent complex [Cu(mal)]n resulting CuO and gaseous products. The mass loss calculated (48.08%) is perfectly match with the observed value of 48.47%. The mass of the residue after the complete decomposition was found to be 26.17% which is in good agreement with the theoretical value of 26.20%. The thermal decomposition features are summarized below and tabulated in Table 6.13.

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

281

, N2
[Cu(en)2]mal.H2O

65 - 100 oC , N2

[Cu(en)2]mal + H2O

.... (6.29)

[[Cu(en)2]mal

185 - 215 o C

[Cu(en)mal] + en

. (6.30)

[Cu(en)mal]

, N2 215 - 350 oC

CuO + en + gaseous products. (6.31)

Table 6.13 Thermal characteristics of [Cu(en)2]mal.H2O

Temp range (0C) 65-100 185-215 [Cu(en)2]mal.H2O 215-350 Above 350 255 III 48.47 26.17 48.08 26.20 eq 6.31 CuO Peak temp (0C) 94 213 Wt. loss (in%) Stages Found I II 5.86 19.50 Calcd 5.93 19.76 Probable reaction eq.6.29 eq 6.30

Compound

(c)

[Cu(bipy)(mal)(H2O)].H2O, 36 The thermogram of the adduct is shown in Fig 6.14. The

thermal decomposition is seen starting at 600C and ending at 1200C, with a Ts of 920C. The loss in mass corresponding to this decomposition amounts to 9.95% which was in good agreement with the theoretical value of 10.06% for the loss of two moles of water (both lattice and coordinated). A well horizontal region in the range 1202200C supports the stability of [Cu(bipy)mal] complex. The second stage of decomposition is seen starting at 2200C and ending at 3000C with a high mass loss. In this stage the loss of one mole of bipy

282

Chapter 6

together with the decomposition of malonate moiety can be expected to takes place to yield CuO and some gaseous products. The weight loss calculated (67.71%) was found to be close match with the observed value of 67.60%. The mass of the residue after the complete decomposition was observed to be 22.45% which was in good agreement with the theoretical value of 22.23%. The decomposition feature are summarized below and tabulated in Table 6.14.

Fig 6.14. The thermogram (TG/DTG) of [Cu(bipy)(mal)(H2O)].H2O in N2

[Cu(bipy)(mal)(H2O)].H2O

, N2 60 - 120 oC

[Cu(bipy)(mal)] + 2H2O ... (6.32)

[Cu(bipy)(mal)]

, N2 220 - 300 oC

CuO + bipy + gaseous products ...(6.33)

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

283

Table 6.14 Thermal characteristics of [Cu(bipy)(mal)(H2O)].H2O

Compound Temp range (0C) 60-120 [Cu(bipy)(mal)(H2O)].H2O 220-300 Above 300 Peak temp (0C) 92 275 Wt. loss (in%) Stages I II Found 9.95 67.60 22.45 (residue) Calcd 10.06 67.71 22.23 (residue) Probable reaction eq.6.32 eq 6.33 CuO

(d)

[Cu(phen)2]mal.2H2O, 37 The thermogram of the adduct is given in Fig 6.15. This

compound is found to be stable only upto 500C and is seen decomposing in three stages with the first one starting at 500C (Ti) and progressing till 1050C (Tf). The weight loss corresponding to this stage amounts to 6.10% agrees well with the calculated value of 6.02% for the loss of 2 moles of lattice water. The second stage of decomposition is seen starting at 1700C and ending at 2950C with a peak temp (Ts) of 2850C. In this stage two moles of phen moieties escapes from the adduct. The third stage of decomposition is seen commencing immediately after the second at 2950C (Ti) and ending at 6500C (Tf) with a peak temp (Ts) of 5850C. This stage is attributed to the decomposition of [Cu(mal)]n to CuO and some gaseous products. The weight loss observed during this stage was 32.90% which does not agrees with the theoretical value of 14.38%. This is because the third stage which is actually getting initiated before completion of the second stage. The residual mass after the complete decomposition was found to be 13.20% is in perfect match with the calculated value of 13.30% expected for CuO. The decomposition features are summarized below and tabulated in Table 6.15.

284

Chapter 6

Fig 6.15 The thermogram (TG/DTG) of [Cu(phen)2]mal.2H2O is N2

[Cu(phen)2]mal.2H2O

, N2 50 - 105 oC

[Cu(phen)2]mal + 2H2O. (6.34)

[Cu(phen)2]mal

, N2 170 - 295 oC

[Cu(mal)]n+ 2 phen

... (6.35)

[Cu(mal)]n

, N2 295 - 650 oC

CuO + gaseous products

.. (6.36)

Table 6.15 Thermal characteristics of [Cu(phen)2]mal.2H2O

Compound Temp range (0C) 50-105 170-295 [Cu(phen)2]mal.2H2O 295-650 Above 650 Peak temp (0C) 102 285 585 Wt. loss (in%) Stages Found 6.10 47.80 32.90 13.20 (residue) Calcd 6.02 66.30 14.38 13.30 (residue) Probable reaction eq. 6.34 eq.6.35 eq. 6.36 CuO

I II III -

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

285

(e)

[Cu(py)(H2O)(mal)]n, 38 From the thermogram given in Fig 6.16, it is observed that

this compound is thermally stable upto 2000C indicated by a well defined plateau. The decomposition is seen starting at 2000C (Ti) and progressing till 3500C with a peak temperature of 2300C (Ts). During this stage the loss of one mole of coordinated water and the escape of one mole of pyridine together with the decomposition of malonate moiety can be expected to take place to yield CuO as the final product. The weight loss corresponding to this stage was found to be 69.67% which is in perfect match with the theoretical value of 69.72%. The mass of the residue after the complete decomposition was observed to be 30.33% which is in good agreement with the theoretical value of 30.28% expected for CuO. Above 3500C, the residue is found to be stable under N2 atmosphere. The decomposition features are given below and tabulated in Table 6.16.

Fig 6.16. The thermogram (TG/DTG) of [Cu(py)(H2O)(mal)]n in N2

, N2

[Cu(py)(H2O)mal]n

200-350 C

CuO + H2O + py. (6.37)

286

Chapter 6

Table 6.16. The thermal characteristics of [Cu(py)(H2O)(mal)]n

Temp range (0C) Peak temp (0C) Wt. loss (in%) Stages Found I 69.67 30.33 (residue) Calcd 69.72 30.28 (residue) Probable reaction eq.6.37 CuO

Compound

200-350 [Cu(py)(H2O)(mal)]n Above 350

230 -

(f)

[Cu(pn)2]mal.2H2O, 39 The thermogram of the adduct is shown in Fig. 6.17. This

compound is found to be stable only upto 500C (Ti) and ending at 800C (Tf). The weight loss corresponding to this stage amounts to 9.82% which agrees with the calculated value of 10.29%. In this the stage the loss of two moles of lattice water takes place from the adduct. The second stage of decomposition is seen initiating at 1800C (Ti) and ending at 2100C (Tf) with a loss in mass of 21.12%. During this stage one mole of pn escapes from the adduct. The weight loss calculated (21.19%) is in good agreement with the observed value of 21.12%. The third stage is seen commencing at 2100C (Ti) and progressing till 5000C (Tf) with a peak temperature of 2200C (Ts). In this stage the loss of one mole of pn together with the decomposition of malonate moiety can be expected to take place to yield CuO as the final product. The residual mass after the complete thermal process was 22.63%, which is in perfect match with the theoretical value of 22.74%. The decomposition features are summarized below and tabulated in Table 6.17.

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

287

Fig. 6.17 The thermogram (TG/DTG) of [Cu(pn)2]mal.2H2O in N2

[Cu(pn)2]mal.2H2O

, N2

50-80 C
[Cu(pn)2]mal
, N2

[Cu(pn)2]mal + 2H2O

.(6.38)

180 - 210 C
[Cu(pn)mal]n
, N2

[Cu(pn)mal]n + pn

... (6.39)

CuO+ pn +gaseous products

0

. (6.40)

210 - 500 C
Table 6.17. The Thermal characteristics of [Cu(pn)2]mal.2H2O
Temp range (0C) 50-80 [Cu(pn)2]mal.2H2O 180-210 210-500 Above 500 Peak temp (0C) 70 190 220 I II III Wt. loss (in%) Stages Found 9.82 21.12 46.43 22.63 (residue) Calcd 10.29 21.19 45.78 22.74 (residue) Probable reaction eq.6.38 eq 6.39 eq.6.40 CuO

Compound

288

Chapter 6

6.2.2 Kinetic Aspects The kinetic parameters like Ea and A were calculated for all the complexes for well defined stages of thermal decomposition from the slope and intercept of linear graphs obtained by plotting g()/T2 vs 1000/T (Fig 6.18-6.20) using CoatsRedfern(11) equation. The goodness of fit was determined from the correlation coefficient calculated. The entropy of activation for each stage of thermal decomposition was also calculated from the relationship A =

kTs S / R e h

-7.5

Lewis-base adducts of 21 Stage 1 b

-6.0 -6.5 -7.0

Lewis-base adducts of 21 Stage 2 c

log [g()/T ]

-8.0

d
-8.5

log [g()/T ]

-7.5 -8.0 -8.5 -9.0 -9.5

c
-9.0

d a
1.6 1.8 2.0 2.2 2.4 2.6

a
-10.0

2.4

2.5

2.6

2.7

2.8

2.9

3.0

3.1

3.2

1000/T

1000/T

(i)
-8.0
-6.5 -7.0 -7.5

(ii)
Lewis-base adducts of 21 Stage 3 a

Lewis - base adducts of 21

-8.2

Stage 4
-8.4

log [g()/T ]

-8.0 -8.5 -9.0 -9.5 -10.0 1.4 1.5 1.6 1.7 1.8 1.9 2.0 2.1

log [g()/T ]

-8.6 -8.8 -9.0 -9.2

d
2.2

-9.4 1.65 1.70 1.75 1.80 1.85 1.90 1.95

d
2.00

1000/T

1000/T

(iii)
)/T2)

(iv)

Fig. 6.18 log (g( vs 1000/T for the thermal decomposition of Lewisbase adducts of nickel(II) malonate 21: (i) Stage 1 (ii) Stage 2 (iii) Stage 3 (iv) Stage 4 (a) [Ni(en)2(H2O)2]mal 24 (b) [Ni(bipy)2(H2O)2]mal 25 (c) [Ni(phen)2mal].3H2O 26 (d) [Ni(pn)2(H2O)2]mal.2H2O 28

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

289

Lewis-base adducts of 22
-8.0

Stage I

-6

Lewis-base adducts of 22 Stage II

-7

b c

log [g()/T ]

log [g()/T ]

-8.5

-8

-9.0

-9

b
-9.5

c
2.6 2.8

a
3.0

-10

d
1.75 1.80 1.85 1.90 1.95 2.00

2.0

2.2

2.4

1000/T

1000/T

(i)

(ii)

-8.0

Lewis-base adducts of 22 Stage III

-8.5

log [g()/T ]

-9.0

-9.5

a
-10.0

b
-10.5 1.0 1.1 1.2 1.3

c
1.4 1.5 1.6 1.7 1.8

1000/T

(iii)
Fig. 6.19 log (g()/T2)vs 1000/T for the thermal decomposition of Lewisbase adducts of cobalt(II) malonate 22: (i) Stage I (ii) Stage II (iii) Stage III (a) [(Co(en)2mal).H2O]n 29 (c) [Co(phen)2(H2O)2]mal 31 (b) [Co(bipy)2(H2O)2]mal 30 (d) [Co(py)(H2O)mal]n 32

290

Chapter 6

-6.0 -6.5 -7.0

Lewis-base adducts of 23 Stage I

Lewis-base adducts of 23
-8.0

Stage II

log [g()/T ]

-8.0 -8.5

log [g()/T ]

-7.5

-8.5

-9.0

c
-9.5

d b

c
-9.0 -9.5 1.8 2.0

f d e
2.2 2.4 2.6 2.8 3.0

b
1.7 1.8 1.9 2.0 2.1

2.2

2.3

1000/T

1000/T

(i)
Lewis-base adducts of 23 Stage III

(ii)

-8.5

-9.0

log [g()/T ]

-9.5

-10.0

f d b

-10.5 1.2 1.4 1.6 1.8 2.0

1000/T

(iii)
Fig. 6.20 log (g()/T2)vs 1000/T for the thermal decomposition of Lewisbase adducts of copper(II) malonate 23 (i) Stage I (ii) Stage II (iii) Stage III (a) [Cu(en)mal] 34 (b) [Cu(en)2]mal. H2O. 35 (c) [Cu(bipy)(H2O) mal].H2O 36 (d) [Cu(phen)2]mal.2H2O 37 (e) [Cu(py)(H2O)mal]n 38 (f) [Cu(pn)2]mal.2H2O 39

(a)

Lewis-base adducts of [Ni(H2O)2mal]n The kinetic parameters for the thermal decomposition stages

of Lewis-base adducts of [Ni(H2O)2mal]n are prosecuted in Table 6.18. The activation energies (Ea) for the different stages of thermal decomposition are in the range 69.19 to 386.87 kJ/mol. The corresponding values of entropy of activation (S) fall in the rage

Thermal Dissociation Features of Malonate Complexes of Ni(II), Co(II) and Cu(II) ..

291

-41.08 to -265.29 J/K/mol. The pre-exponential factors vary in the range 0.17-8.32 1010 s-1. There is no definite trend either in the values of Ea or in the values of S. The negative values of S
(12-14)

indicate that the activated complex has a more ordered structure than the reactants and the reaction are slower than normal. (b) Lewis-base adducts of [Co(H2O)2mal]n The kinetic parameters calculated for the thermal

decomposition stages of all the adducts of [Co(H2O)2mal]n are presented in Table 6.19. The activation energies (Ea) for the different stages of thermal decomposition are in the range 47.18 to 408.12 kJ/mol. The corresponding values of entropy of activation (S) fall in the range -33.71 to -262.52 J/K/mol. The pre-exponential factors vary in the range 0.16-1.82 1010 s-1 (c) Lewis-base adducts of [Cu(H2O)2mal]n The kinetic parameters calculated for the thermal

decomposition stages of all the adducts of [Cu(H2O)2mal]n are presented in Table 6.20. The activation energies (Ea) for the different stages of thermal decomposition are in the range 53.26 to 409.16 kJ/mol. The corresponding values of entropy of activation (S) fall in the range -31.73 to -292.33 J/K/mol. The pre-exponential factors vary in the range 0.08 to 3.45 1010 s-1. 6.2.3 Mechanistic Aspects The elucidation of the mechanistic of solid state thermal decomposition of Lewis-base adducts of [M(H2O)2mal]n [M = Ni+2, Co+2 and Cu+2] was done by using the nine equations suggested by Satava.(15,16) The form of g() which gives the best representation of

292

Chapter 6

experimental data is considered as the mechanism of the reaction. The correlation coefficients obtained for the nine forms of g() for the various stages of thermal decompositions of the complexes are presented in Tables 6.21-6.27.

Table 6.18. Kinetic parameters for the thermal decomposition stages of Lewis-base adducts of nickel(II) malonate

Stage I Compound Ea kJ/mol S J/K/ mol Ea kJ/ mol

Stage II S J/K/mol Ea kJ/mol

Stage III S J/K/ mol Ea kJ/mol

Stage IV S J/K/ mol

A s-1

A s-1

A s-1

A s-1

[Ni(en)2(H2O)2]mal

73.61

6.3647

-231.82

275.93

1.922 109

-71.88

317.97

8.321010

-41.08

[Ni(bipy)2(H2O)2]mal

108.9

1553.79

-186.06

305.62

2.422 1010

-51.43

[Ni(phen)2mal].3H2O

73.13

45.74

-213.75

86.35

7.14

-234.44

[Ni(pn)2(H2O)2]mal.2H2O

103.85

2660.18

-178.19

69.19

1.33

-245.83

386.87

8.021010

-50.81

70.32

0.17

-265.29

294

Table 6.19

Kinetic parameters for the thermal decomposition stages of Lewis-base adducts of cobalt(II) malonate
Stage I Stage II S J/K/mol -262.52 Ea kJ/mol 195.66 A s-1 423697 S J/K/mol -141.95 Ea kJ/mol 349.35 Stage III A s-1 1.82 1010 S J/K/ mol -54

Compound

Ea kJ/mol 47.18

A s-1 0.16

[(Co(en)2mal).H2O]n

[Co(bipy)2(H2O)2]mal

152.12

998203.1

-132.09

205.93

2834180

-126.49

259.78

4718085

-122.91

[Co(phen)2(H2O)2]mal

112.09

2595.15

-181.73

251.26

7.08107

-99.95

[Co(py)(H2O)mal]n

93.25

15.08

-226.33

242.74

9028181

-116.55

408.12

1.461010

-33.71

295

Table 6.20. Kinetic parameters for the thermal decomposition stages of Lewis-base adducts of copper (II) malonate
Compound Ea kJ/mol [Cu(en)mal] 166.22 Stage I A s-1 48727.84 S J/K/mol -159.98 Ea kJ/mol Stage II A s-1 S J/K/mol Ea kJ/mol Stage III A s-1 S J/K/mol -

[Cu(en)2]mal.H2O

107.45

2666.91

-181.91

175.42

118582.7

-151.77

104.54

1.53

-247.09

[Cu(bipy)(mal)(H2O)].H2O

98.17

1086.96

-188.47

152.64

1914.47

-187.07

[Cu(phen)2]mal.2H2O

53.26

0.275

-257.71

57.22

0.08

-271.22

61.75

9.23 103

-292.33

[Cu(py)(H2O)mal]n

369.72

1.681010

-47.75

[Cu(pn)2]mal.2H2O

113.93

37983.77

-158.41

130.07

1844.39

-185.90

409.16

3.45 1010

-31.73

296

Table 6.21
Form of g() 2 +(1-) ln(1-) [1-(1-)1/3]2 (1- 3 )-(1-)2/3 -ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3
2

Correlation coefficients calculated using the nine forms of g() for the Lewis base adducts of nickel(II) and cobalt(II) malonate stage I
[Ni(bipy)2 (H2O)2]mal -0.992437 -0.9926390 -0.990024 -0.9926420 -0.991866 -0.9893390 -0.985703 -0.991611 -0.991796 [Ni(phen)2mal].3H2O -0.988107 -0.988623 -0.983065 -0.988814 -0.987916 -0.982609 -0.974077 -0.986946 -0.987254 [Ni(pn)2(H2O)2]mal.2H2O -0.996845 -0.997157 -0.996632 -0.997139 -0.997190 -0.996115 -0.993920 -0.996855 -0.996679 [(Co(en)2mal). H2O]n -0.997385 -0.997404 -0.995645 -0.997408 -0.996661 -0.993885 -0.981404 -0.996663 -0.9976674 [Co(bipy)2(H2O)2]mal -0.982047 -0.982281 -0.978849 -0.982394 -0.981469 -0.978211 -0.973497 -0.981050 -0.981109 [Co(phen)2 (H2O)2]mal -0.991608 -0.991829 -0.989260 -0.991930 -0.991342 -0.988655 -0.985109 -0.990880 -0.990939 [Co(py)(H2O)mal]n -0.991349 -0.991882 -0.987262 -0.992038 -0.991331 -0.986728 -0.977778 -0.990526 -0.990859

[Ni(en)2 (H2O)2]mal -0.991580 -0.991924 -0.987300 -0.992016 -0.990638 -0.985885 -0.975407 -0.9903580 -0.990466

297

Table 6.22 Correlation coefficients calculated using the nine forms of g() for the Lewis-base adducts of nickel(II) and cobalt(II) malonate (Stage II)
Form of g() 2 +(1-) ln(1-) [1-(1-)1/3]2 (1- 3 )-(1-)2/3 -ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3
2

[Ni(en)2 (H2O)2]mal -0.991509 -0.991593 -0.990745 -0.991748 -0.990721 -0.989536 -0.988098 -0.990977 -0.990876

[Ni(bipy)2 (H2O)2]mal -0.992582 -0.992996 -0.992158 -0.993084 -0.993579 -0.993307 -0.993316 -0.992793 -0.993065

[Ni(phen)2 mal].3H2O -0.9959750 -0.996227 -0.995697 -0.996142 -0.996928 -0.995872 -0.996331 -0.996316 -0.9962030

[Ni(pn)2(H2O)2] mal.2H2O -0.996276 -0.996439 -0.993828 -0.996525 -0.995764 -0.992613 -0.984096 -0.995516 -0.995627

[(Co(en)2 mal). H2O]n -0.972875 -0.974188 -0.967362 -0.974580 -0.974546 -0.969235 -0.962267 -0.972503 -0.973182

[Co(bipy)2 (H2O)2]mal -0.9856 -0.990761 -0.989058 -0.990947 -0.991747 -0.990857 -0.990006 -0.990577 -0.991372

[Co(phen)2 (H2O)2]mal -0.991973 -0.992163 -0.991345 -0.992161 -0.992290 -0.991187 -0.990421 -0.991628 -0.991863

[Co(py) (H2O) mal]n -0.994025 -0.994256 -0.993213 -0.994308 -0.994127 -0.992979 -0.992104 -0.994089 -0.994044

Table 6.23

Correlation coefficients calculated using the nine forms of g() for the Lewis-base adducts of nickel(II) and cobalt(II) malonate (Stage III)
[Ni(en)2(H2O)2] mal -0.989456 -0.989641 -0.988731 -0.989908 -0.990330 -0.989584 -0.988541 -0.989364 -0.989521 [Ni(pn)2(H2O)2] mal.2H2O -0.999106 -0.998916 -0.998785 -0.999262 -0.998746 -0.998229 -0.997097 -0.998959 -0.998786 [(Co(en)2mal).H2O]n -0.991851 -0.991849 -0.990754 -0.991898 -0.991514 -0.990462 -0.989762 -0.991482 -0.991624 [Co(bipy)2 (H2O)2]mal -0.986201 -0.986346 -0.984072 -0.9865480 -0.985679 -0.9828730 -0.980374 -0.985351 -0.9853375

Form of g()

2 +(1-) ln(1-) [1-(1-)1/3]2

2/3 (1- 2 3 )-(1-)

-ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3

300

Table 6.24

Correlation coefficients calculated using the nine forms of g() for the Lewisbase adducts of nickel(II)) malonate stage IV Form of g() 2 +(1-) ln(1-) [1-(1-)1/3]2
2/3 (1- 2 3 )-(1-)

[Ni(pn)2(H2O)2]mal.2H2O -0.991152 -0.991293 -0.982548 -0.991303 -0.988640 -0.976253 -0.932184 -0.988263 -0.988399

-ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3

Table 6.25 Correlation coefficients calculated using the nine forms of g() for the Lewis-base adducts of copper(II) malonate (Stage I)
Form of g() 2 +(1-) ln(1-) [1-(1-)1/3]2
2/3 (1- 2 3 )-(1-)

[Cu(en)mal] -0.992041 -0.992259 -0.991029 -0.992436 -0.992443 -0.991712 -0.991038 0.992060 0.992176

[Cu(en)2] mal.H2O -0.993494 -0.993644 -0.991581 -0.993746 -0.993388 -0.991683 -0.988898 -0.993012 -0.993226

[Cu(bipy)(mal) (H2O)].H2O -0.995936 -0.996142 -0.994345 -0.996180 -0.995990 -0.994831 -0.992867 -0.995761 -0.995823

[Cu(phen)2] mal.2H2O -0.995591 -0.995884 -0.991539 -0.995982 -0.995032 -0.989229 -0.971989 -0.994534 -0.994682

[Cu(py) (H2O)mal]n -0.993536 -0.993740 -0.992919 -0.993759 -0.993735 -0.993018 -0.992408 -0.993449 -0.993384

[Cu(pn)2] mal.2H2O -0.996978 -0.997013 -0.996631 -0.997022 -0.996393 -0.995639 -0.994226 -0.996714 -0.996616

-ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3

Table 6.26

Correlation coefficients calculated using the nine forms of g() for the Lewisbase adducts of copper(II) malonate stage II
[Cu(en)2 mal.H2O] -0.999357 -0.999476 -0.999092 -0.999497 -0.999467 -0.999048 -0.999125 -0.999236 -0.999423 [Cu(bipy)(mal) (H2O)].H2O -0.986211 -0.986636 -0.982028 -0.986780 -0.985791 -0.981295 -0.974980 -0.985160 0.985306 [Cu(phen)2] mal.2H2O -0.994846 -0.995131 -0.988167 -0.995191 -0.993739 -0.984251 -0.939410 -0.993188 -0.993324 [Cu(pn)2] mal.2H2O -0.996729 -0.996841 -0.995526 -0.996920 -0.996896 -0.996097 -0.994198 -0.996536 -0.996713

Form of g() 2 +(1-) ln(1-) [1-(1-)1/3]2 (12 3

)-(1-)2/3

-ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3

Table 6.27

Correlation coefficients calculated using the nine forms of g() for the Lewisbase adducts of copper(II) malonate stage III
[Cu(en)2]mal.H2O -0.998784 -0.998869 -0.997764 -0.998909 -0.998636 -0.997642 -0.995994 -0.998512 -0.998458 [Cu(phen)2]mal.2H2O -0.982475 -0.982955 -0.945669 -0.983159 -0.973329 -0.897294 -0.969319 -0.971932 -0.972422 [Cu(pn)2]mal.2H2O -0.995838 -0.995768 -0.995185 -0.995551 -0.995551 -0.995262 -0.994973 -0.995538 -0.995737

Form of g() 2 +(1-) ln(1-) [1-(1-)1/3]2 (12 3

)-(1-)2/3

-ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3

303

From the tables, it is evident that the rate determining process during the thermal decomposition of the complexes is represented corresponding by to g()=(1-2/3)-(1-)2/3 GinstlingBrownshtein in most of cases three equation

dimensional diffusion, spherical symmetry. But in certain other cases the rate controlling process corresponding to Random nucleation, one nucleus on each particle; obeying Mampel equation.(16) The forms of g() with the highest value of correlation coefficients and the corresponding rate controlling process are tabulated and are presented in Tables 6.28 6.37. Table 6.28 The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of nickel(II) malonate Stage I
Compound Form of g() Rate controlling process Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation Random nucleation, one nucleus on each particle, Mampel equation

[Ni(en)2(H2O)2]mal

2/3 (1- 2 3 )-(1-)

[Ni(bipy)2(H2O)2]mal

(1-

2 3

)-(1-)2/3

[Ni(phen)2mal].3H2O

(1-

2 3

)-(1-)2/3

[Ni(pn)2(H2O)2]mal.2H2O

-ln(1-)

304

Table 6.29 The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of nickel(II) malonate Stage II
Compound Form of g() Rate controlling process Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation Random nucleation, one nucleus on each particle, Mampel equation Random nucleation, one nucleus on each particle, Mampel equation Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation

[Ni(en)2(H2O)2]mal

(1-

2 3

)-(1-)2/3

[Ni(bipy)2(H2O)2]mal

-ln(1-)

[Ni(phen)2mal].3H2O

-ln(1-)

[Ni(pn)2(H2O)2]mal.2H2O

2/3 (1- 2 3 )-(1-)

Table 6.30 The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of nickel(II) malonate Stage III
Compound Form of g() Rate controlling process Random nucleation, one nucleus on each particle, Mampel equation Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation

[Ni(en)2(H2O)2]mal

-ln(1-)

[Ni(pn)2(H2O)2]mal.2H2O

(1-

2 3

)-(1-)2/3

305

Table 6.31 The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of nickel(II) malonate Stage IV
Compound [Ni(en)2(H2O)2]mal [Ni(bipy)2(H2O)2]mal [Ni(phen)2mal].3H2O Form of g() Rate controlling process Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation

[Ni(pn)2(H2O)2]mal.2H2O

(1-

2 3

)-(1-)2/3

Table 6.32

The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of cobalt(II) malonate Stage I
Form of g() Rate controlling process Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation

Compound

[(Co(en)2mal).H2O]n

(1-

2 3

)-(1-)2/3

[Co(bipy)2(H2O)2] mal [Co(phen)2(H2O)2]mal [Co(py)(H2O)mal]n

2/3 (1- 2 3 )-(1-)

2/3 (1- 2 3 )-(1-)

2/3 (1- 2 3 )-(1-)

306

Table 6.33

The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of cobalt(II) malonate Stage II

Compound

Form of g()

Rate controlling process Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation Random nucleation, one nucleus on each particle, Mampel equation Random nucleation, one nucleus on each particle, Mampel equation Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation

[(Co(en)2mal).H2O]n

(1-

2 3

)-(1-)2/3

[Co(bipy)2(H2O)2]mal

-ln(1-)

[Co(phen)2(H2O)2]mal

-ln(1-)

[Co(py)(H2O)mal]n

2/3 (1- 2 3 )-(1-)

Table 6.34

The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of cobalt(II) malonate Stage III
Form of g() Rate controlling process Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation

Compound

[(Co(en)2mal).H2O]n

(1-

2 3

)-(1-)2/3

[Co(bipy)2(H2O)2]mal

2/3 (1- 2 3 )-(1-)

307

Table 6.35
,

The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of copper(II) malonate Stage I
Form of g() Rate controlling process Random nucleation, one nucleus on each particle, Mampel equation Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation

Compound

[Cu(en)mal]

-ln(1-)

[Cu(en)2]mal.H2O [Cu(bipy)(mal)(H2O)].H2O [Cu(phen)2]mal.2H2O [Cu(py)(H2O)mal]n [Cu(pn)2]mal.2H2O

(1-

2 3

)-(1-)2/3

2/3 (1- 2 3 )-(1-) 2/3 (1- 2 3 )-(1-) 2/3 (1- 2 3 )-(1-) 2/3 (1- 2 3 )-(1-)

Table 6.36 The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of copper(II) malonate Stage II
Compound Form of g() Rate controlling process Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation

[Cu(en)2]mal.H2O [Cu(bipy)(mal)(H2O)].H2O [Cu(phen)2]mal.2H2O [Cu(py)(H2O)mal]n [Cu(pn)2]mal.2H2O

2/3 (1- 2 3 )-(1-)

2/3 (1- 2 3 )-(1-) 2/3 (1- 2 3 )-(1-)

2/3 (1- 2 3 )-(1-)

308

Table 6.37 The form of g() with the highest value of correlation coefficient and the corresponding rate controlling process for Lewis-base adducts of copper(II) malonate Stage III.
Compound Form of g() Rate controlling process Three dimensional diffusion, spherical symmetry, Ginstling-Brownshtein equation

[Cu(en)2]mal.H2O [Cu(phen)2]mal.2H2O [Cu(pn)2]mal.2H2O

(1-

2 3

)-(1-)2/3

2/3 (1- 2 3 )-(1-) 2/3 (1- 2 3 )-(1-)

6.2.4 Trend in thermal behaviour of metal malonates and their adducts

It was seen in metal succinate systems that the stability towards the thermal decomposition in them is in the order [Cu(suc)]n < (Ni(H2O)2(suc)).2H2O]n < [Co(suc)]n.2H2O, which was explained in terms of Irving-William order that demands stronger Cu-O bond than Ni-O and Co-O bond (see Section 4.2.4 for details). In contrast to this, metal malonates have thermal stability in the order [Co(H2O)2(mal)]n (2700C) < [Ni(H2O)2(mal)]n (2750C) the < [Cu(H2O)2(mal)]n (2850C), which appear contrary to the above argument. This trend could be explained by considering differences in the ligation mode of malonate in them. The spectral data show that in [Ni(H2O)2(mal)]n, 21 and [Co(H2O)2(mal)]n, 22, the malonate moiety is bidentatively chelating while in 23, it is in the monodentate form. The closer interaction of the carboxylate moiety in chelating mode with the metal in 21 and 22 makes the decomposition easy in them than in 23 where the carboxylate moieties is in the monodentate form. Table 6.38 shows the thermal

309

data associated with Lewis-base dissociation in the adducts of various metal malonates. Among the adducts of nickel(II) malonate, the pn adduct 28 is found to be more stable (in the dissociation of first Lewis-base moiety) than the en adduct 24. Both Ea and S associated with this thermal step are also in agreement with the expectation. In bipy adduct 25 and phen adduct 26, we do not see any thermal step associated with the loss of Lewis-base alone but a combined loss of the Lewis-base and the malonate moiety only at 290 and 3100C respectively. The apparent anomaly observed in the Ea and S values of these adducts can be explained by considering the ionic form of mal moiety in 25 and its coordinated form in 26. As expected, the stability of the adducts of cobalt(II) malonate towards the Lewis-base decomposition is seen to be in the order 32 < 29 < 30 < 31 (for py, en, bipy and phen dissociation respectively), as observed in the case of nickel(II) malonate adducts. The Ea and S associated with this thermal steps are also consistent with the expected trend. In the case of copper(II) malonate, we find that the dissociation of first pn and en moiety in 39 and 35 occurs at comparable temperatures. The Ea and S associated with this thermal steps are also consistent with the above observation. In 34, 36 and 38 which contain malonate moiety in coordinated form and have one bonded Lewis-base moiety are seen to decompose in single step (Table 6.38). In 37, we find the combined dissociation of both the phen moieties in a single step at 1700C and the Ea and S values associated with this thermal step are seen to be consistent with the observation.

310

Table 6.38

Thermal data associated with the Lewis-base dissociation in the adducts of metal(II) malonates
Ti of Lewisbase loss (0C) 175 290* 310* 190 220 230 275* 145 245* 185 220* 170 200* 180 Ti of final stage (0C) 260* 200* 280 280 270 215* 295 210* S (J/K/mol) -71.88 -51.43* -234.44* -50.81 -141.95 -126.49 -99.95* -226.33 -159.98* -151.77 -187.07* -271.22 -47.75* -185.90

Adducts [Ni(en)2(H2O)2]mal 24 [Ni(bipy)2(H2O)2]mal 25 [Ni(phen)2mal].3H2O 26 [Ni(pn)2(H2O)2]mal.2H2O 28 [(Co(en)2 mal).H2O]n 29 [Co(bipy)2(H2O)2]mal 30 [Co(phen)2(H2O)2]mal 31 [Co(py)(H2O)mal]n 32 [Cu(en)mal] 34 [Cu(en)2]mal.H2O 35 [Cu(bipy)(mal) H2O] .H2O 36 [Cu(phen)2] mal.2H2O 37 [Cu(py)(H2O)mal]n 38 [Cu(pn)2]mal.2H2O 39

Ea (kJ/mol) 275.93 305.62* 86.35* 386.87 195.66 205.93 251.26* 93.25 166.22* 175.42 152.64* 57.22 369.72* 130.07

* combined decomposition of Lewis-base + malonate moiety Ea : activation energy associated with dissociation of first Lewis-base moiety S: entropy change associated with dissociation of first Lewis-base moiety

311

References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. F. P. Cavasino, J. Phys. Chem; 69 (1965) 4380 H. Hoffman, J. Steuhr, J. Phys. Chem; 70 (1966) 955 J. L. Bear and C. T. Lin, J. Phys. Chem; 72 (1968) 2026 Y. Suzuki and K. Muraishi, Thermochim. Acta; 255 (1995) 155 I. G. D. Muro, M. Insausti and L. Lezama, Euro. J. Inorg chem.; (1999) 935 M. A. Mohamed, A. K. Galway and S. A. Halaway, Thermochim. Acta; 346 (2000) 91 M. A. Mohamed, A. K. Galwey and S. A. Halawy, Thermochim. Acta; 323 (1998) 27 U. B. Ceipidor, M. Tomassetti and E. Cardarelli, Thermochim. Acta; 30 (1979) 15 A. K. Nikumbh, S. K. Pardeshi and M. N. Raste, Thermochim. Acta; 374 (2001) 115 B. N. Sivasankar and S. Govindarajan, J. Therm. Anal; 48 (1997) 1401 A. W. Coats and J. P Redfern, Nature; 201 (1964) 68 A. A. Fraost and R. G. Pearson, Kinetics and Mechanism, Wiley, New York; (1961) T. Gangadevi, K. Muraleedharan and M. P Kannan, Thermochim. Acta; 146 (1989) 225 K. K. Aravindakshan and K. Muraleedharan, Thermochim. Acta; 155 (1989) 247 V. Satava, Thermochim. Acta; 2 (1971) 423 C. G. R Nair, S. Mathew and K. N Ninan, Thermochim. Acta; 150 (1989) 63

Chapter 7 Interaction of Lewis-bases with Polymeric Metal(II) Oxalates

7.1

Introduction
xalic acid, (H2ox), HOOC-COOH, can be considered as the simplest of all dicarboxylic acids. The structure involves simply two -COOH groups connected directly through the

two carboxyl carbon atoms and has got unique electronic structure quite different from that of both succinic (H2suc) and malonic Not only this molecule lacks any spacer function

(H2mal) acids.

between the carboxylic groups but also it has got connectivity through two sp2 hybridized C atoms. Consequently its dianion, -OOC-COO-, has conjugation extended over all the 6 atoms forming a perfect planar configuration. This is one main feature that distinguishes the oxalate moiety from its counterparts mentioned in earlier chapters. Though, in principle, oxalate moiety can take part in coordination involving various linking modes referred earlier, the predominant ligation mode is seen to be mostly bisbidentate bridging type (see Chapter 1, Section 1.2, for details). This makes the oxalate moiety a very strong bridging ligand through -coordination resulting in polymeric metal carboxylates with rigid 1D, 2D or 3D framework structures. Interesting feature in these extended structures is the -electron delocalisation possible along the whole metal-oxalate framework both through pp and p-d interactions. Such interactions result in an effective metal to metal electronic communication via the conjugated oxalate function leading to interesting magnetic and electronic properties. Many metal oxalate structures are reported in the

literature including those occurring naturally as minerals.(1) The 2D honey-comb(2,3) structure is seen to be the most common for the oxalates which allows for large variations in molecule type and pore

312

Chapter 7

functionalization. The 1D coordination polymer NH4[Ti(ox)2].2H2O is seen to contain the cyclic tetranuclear [Ti4O4(ox)8]8- ion units and are used as basic building blocks.(4) The first example of an oxalato-uranylate, Na2[(UO2)4(ox)5(H2O)2].8H2O(5) has a zeolite-type structure. A series of open-framework oxalates containing zirconium and cadmium or lead along with alkali-metal or ammonium cations have give also 3D been open reported.(6) frameworks. These In compounds contain MO8 and polyhedral units that are linked through oxalate oxygen atoms to (NH4)2[CdZr(ox)4].3.9H2O right-handed [H3N(CH2)2NH3][CdZr(ox)4].4.4H2O, metal-oxalate

helical wires are formed through connectivity between the oxalate ions and the MO8 polyhedra (M = Cd, Zr).(6a) The oxalate unit serves to link the chains together to yield a 3D structure with channels. Tamaki and co-workers have prepared 2D mixed-metal oxalates with CrIII centers.(7) The [Cr(ox)3]3- ion acts as a building block by binding to three MII centers (M = Fe, Co, Ni, Cu and Zn) ions through oxalate-ion bridges, forming an extended network. An interesting ion-pair [Cu(bipy)2(CH3COO)]+[Cu(bipy)2Cr(ox)3]-.10.5H2O(8) has been reported as the first compound containing the [Cr(ox)3]3- units as monodentate ligands. These complexes form examples in the design and tuning of molecular components in extended structures to attain desirable properties. Recently Arco et al(9) has reported the intercalation of [Cr(ox)3]3- complexes in Mg, Al layered double hydroxides. Mixed-valent oxalates A[MII-MIII(ox)3] (A = monocation; MII = Mn, Fe, Co, Ni, Cu and Zn; MIII= Cr, Fe and Co) have distinct magnetic properties, varying from paramagnetic to ferromagnetic or antiferromagnetic.(10-15) Chiral metal complexes have also been made use of to form layered magnets with oxalate networks and 3D anionic networks as in [(ZII(bipy)3)[MIMIII(ox)3]] or

Interaction of Lewis-bases with Polymeric Metal Oxalates

313

[(ZII(bipy)3)(MIIMIII(ox)3)] (bipy = 2,2'-bipyridyl; ZII = Fe, Co, Ni, Ru and Zn; MI = alkali metal, NH4+; MII = Mn, Fe, Co and Cu; MIII = Cr and Fe).(16) Other interesting 2D ternary complexes reported are [Cu(ox)(L)(H2O)].nH2O(17) (L = bipy, phen and n-phen; n = 1, 2), [M(ox)L]n(18) [L = 4,4'-bipy; M = Co(II), Fe(II), Ni(II) and Zn(II)) and [M(ox)(L)2].nH2O(19) (n = 4,5; M = Ni, Cu; L = bipy or phen) in which the oxalate anions are found to function as bidentate bridging moieties. In [Cu(bipy(ox)].2H2O,(20) the oxalate anions are centrosymmetric and act as quadridentate bridging ligands resulting in zigzag polymeric structure whereas [Cu2(bipy)2(H2O)2(NO3)2(ox)](21) has the unusual ligand arrangement and the packing of molecules are attributed to intermolecular and intramolecular hydrogen bonding leading to a zigzag chain which exhibits antiferromagnetism. In [Cu(en)2][Cu(ox)2],(20a) the oxalate anions act as tridentate moieties. The 1D complex, {[Cu(bipy)(ox)]2.5H2O}n(22) consists of columnar stacks of neutral [Cu(ox)(bipy)] units, exhibiting alternating ferro-antiferromagnetic interactions. The 3D supramolecular complex, K[Cu(trans[14]dien)][Cr(ox)3](23) has been reported, which has large helical tunnels that are formed by the oxalate-bridged, octahedrally coordinated Cr and K centers. In the iron oxalate, (NH4)2[Fe2O(ox)2Cl2].2H2O,(24) a 3D structure with helical tunnels occupied by guest species has been reported. In the iron(III) system, [(acac)2Fe(ox)Fe(acac)2], Fujino et al(25) reported the stabilization of Fe(III) to Fe(II) mixed valence state by the electronic delocalisation through the oxalate bridge. A hydrothermally prepared 1D oxalate, Na2[Co2(ox)3(H2O)2],(26) is known to possesses a ladder-like An topology, interesting which sheet manifests like antiferromagnetic complex, ordering. polymeric

[NaCr(bipy)(ox)2(H2O)].2H2O has been reported by Munoz et al(27)

314

Chapter 7

and observed that oxalate ligands function as monodentate as well as bis-chelating within the chain, showing antiferromagnetic property. On the other hand, Ba4[{Fe(ox)(OH)}4(ox)Cl2](28) possesses two distinct channels (concave and convex) formed by the linking of vertex-sharing FeO6 octahedra through -OH bridges and oxalate ions in a monodentate fashion. Recently Pointillart et al(29) has reported an interesting three-dimensional oxalate-based complexes, {[Ru(bipy)3][Cu2xNi2(1-x)(ox)3]}n (0 x 1) where Cu(II) has unusual tris(bischelated) environment and the compounds are found to be isostructural, single-phased and at low temperature seen to exhibit long-range complexes ordered react magnetic with the behaviour. binuclear Several nickel cyanogold complex, di- or

[{Ni(dien)(H2O)}2(ox)](PF6)2.2H2O(30) resulting in a variety of

polynuclear compounds which show antiferromagnetic behaviour. The use of metal oxalate complexes of Cr, Fe, Mn, Co and Al as novel inorganic dopants is well documented.(31) In the present study we discuss in detail the interaction of Lewis-bases with polymeric metal oxalates and formation and characterisation of various mixed ligand complexes.

7.2

Experimental

7.2.1 Preparation of oxalate complexes of divalent metal ions Metal oxalates of Ni(II), Co(II) and Cu(II) were prepared by reacting the appropriate metal carbonate with a hot aqueous solution of oxalic acid in stoichiometric quantities. The complexes were separated by filtration. These were washed repeatedly with hot water and methanol and dried under vacuum over P2O5.

Interaction of Lewis-bases with Polymeric Metal Oxalates

315

(a)

Nickel(II) oxalate complex, [Ni(H2O)2(ox)]n,

40

To an aqueous solution of oxalic acid (0.13g, 1mM), nickel carbonate (0.37g, 1mM) was added slowly with stirring. Brisk effervescence formed indicating the complex formation. The reaction mixture was boiled on a steam bath for about 30 min. The amount of nickel carbonate added was slightly less than the stoichiometric amount of oxalic acid. The light green complex formed was filtered and washed repeatedly with hot water to remove any excess acid present and finally with methanol. The pure complex thus obtained was dried in vacuo. (yield : 90%) (b) Cobalt(II) oxalate complex, [Co(H2O)2(ox)]n, 41 Cobalt carbonate (0.11g, 1mM) was added in small quantity with stirring to a hot aqueous solution of oxalic acid (0.13g, 1mM). The reaction mixture was boiled on a steam bath for about 1h. The rose complex formed was filtered and washed repeatedly with hot water to remove any excess acid present and finally with methanol. The pure complex thus obtained was dried in vacuo. (yield : 90%) (c) Copper(II) oxalate complex [Cu(ox)]n, 42 The procedure adopted for the preparation of copper(II) oxalate complex was almost the same as that of nickel(II) or cobalt(II) complex. About 0.23g (1mM) of cupric carbonate was added in small quantity to a hot aqueous solution of 0.13g (1mM) oxalic acid while stirring. The light blue complex formed was filtered and washed repeatedly with hot water to remove excess acid and finally with methanol. It was dried under vacuum over P2O5. (yield : 85%)

316

Chapter 7

7.2.2 Preparation of Lewis-base adducts of nickel(II) oxalate (a) [Ni(en)(ox)]n, 43 A solution of en (0.19ml, 3mM) in methanol was added dropwise to a suspension of nickel(II) oxalate (0.18g, 1mM) in methanol with constant stirring for about 2 h. The complex gets separated out as rose violet solid. This was filtered and was repeatedly washed with ether and dried in vacuo. (yield : 80%) (b) [Ni(bipy)(ox)]n, 44 A solution of 2,2'-bipy (0.47g, 3mM) in methanol was added dropwise to a suspension of nickel(II) oxalate (0.18g, 1mM) in methanol. The mixture was kept under reflux for about 2 h. The complex separated out as light violet solid was filtered. This was repeatedly washed with ether and dried under vacuum over P2O5. (yield : 80%) (c) [(Ni(phen)(ox)).2H2O]n, 45 A solution of 1,10-phen (0.6g, 3mM) in methanol was added dropwise to a suspension of nickel(II) oxalate (0.18g, 1mM) in methanol. The mixture was kept under reflux for about 2 h. The complex separated out as light violet solid was filtered. This was washed with methanol followed by ether which was then dried in vacuo. (yield :75%) (d) [Ni(py)2(ox)]n, 46 An excess of pyridine was added to a nickel(II) oxalate (0.36g, 1mM) suspension in methanol with constant stirring. The reaction mixture was refluxed for about 2 h. The complex separated

Interaction of Lewis-bases with Polymeric Metal Oxalates

317

out as light green solid was filtered and repeatedly washed with methanol followed by ether. This was dried in vacuo. (yield :75%) (e) [(Ni(pn)(ox)).H2O]n, 47 A solution of pn (0.27ml, 3mM) in methanol was added dropwise to a suspension of nickel(II) oxalate (0.18g, 1mM) in methanol with constant stirring for about 2 h. A clear blue solution was obtained from which solid blue complex was seen to be separating out soon, making the supernatant liquid colourless. The solid complex was filtered and repeatedly washed with methanol followed by acetone. This was dried in vacuo. (yield : 80%) 7.2. 3 Preparation of Lewis-base adducts of cobalt(II) oxalate (a) [(Co(en)(ox)).H2O]n, 48 A solution of en (0.19ml, 3mM) in methanol was added to a suspension of cobalt(II) oxalate (0.18g, 1mM) in methanol with constant stirring followed by refluxing for about 2 h. The complex separated out as brown solid was filtered and repeatedly washed with methanol followed by ether. This was dried in vacuo. (yield : 80%) (b) [Co(bipy)(ox)]n, 49

To a suspension of cobalt(II) oxalate (0.18g, 1mM) in methanol, a solution of 2,2'-bipy (0.47g, 3mM) in methanol was added. 2 h. The reaction mixture was kept under reflux for about The complex separated out as orange solid was filtered.

This was repeatedly washed with methanol followed by ether. This was then dried in vacuo. (yield : 80%)

318

Chapter 7

(c)

[(Co(phen)(ox)).H2O]n, 50 A solution of phen (0.6g, 3mM) in methanol was added to a

suspension of cobalt(II) oxalate (0.18g, 1mM) in methanol. The mixture was kept under reflux for about 2 h. The complex separated out as orange solid was filtered and repeatedly washed with methanol followed by ether. This was dried in vacuo. (yield : 85%) (d) [Co(py)2(ox)]n, 51 An excess of pyridine was added to a cobalt(II) oxalate (0.36g, 1mM) suspension in methanol with constant stirring. The reaction mixture was refluxed for about 2 h. The complex separated out as light pink solid was filtered and repeatedly washed with methanol followed by diethyl ether. It was dried in vacuo. (yield : 75%) (e) [Co(pn)(ox)]n, 52 A solution of pn (0.48ml, 3mM) in methanol was added dropwise to a suspension of cobalt(II) oxalate (0.36g, 1mM) in methanol with constant stirring for about 2 h. The complex was separated out as dark pink solid which was filtered and repeatedly washed with methanol followed by acetone. vacuo.(yield : 85%) 7.2.4 Preparation of Lewis- base adducts of copper(II) oxalate (a) [(Cu(en)(ox)).2H2O]n, 53 A solution of en (0.19ml, 3mM) in methanol was added dropwise to a suspension of copper(II) oxalate (0.15g, 1mM) in methanol with constant stirring for about 1 h. The complex separated This was dried in

Interaction of Lewis-bases with Polymeric Metal Oxalates

319

out as violet solid was filtered and repeatedly washed with methanol followed by ether. This was dried in vacuo. (yield : 80%) (b) [Cu(bipy)(ox)]n, 54 To a suspension of copper(II) oxalate (0.15g, 1mM) in methanol , a solution of bipy (0.47g, 3mM) in methanol was added. The mixture was kept under reflux for about 2 h. The complex separated out as light blue solid was filtered and repeatedly washed with methanol followed by ether. Finally it was dried in vacuo. (yield : 80%) (c) [Cu(phen)(ox)]n, 55 The method adopted for the preparation of this compound was almost same as that employed for the 2,2'-bipy adduct. The complex was separated out as light blue solid which was then filtered and repeatedly washed with methanol followed by ether. This was dried in vacuo. (yield : 80%) (d) [Cu(py)2(ox)]n, 56 An excess of pyridine was added to a copper(II) oxalate (0.15g, 1mM) suspension in methanol with constant stirring. The reaction mixture was refluxed for about 2 h. The complex separated out as light blue solid was filtered and repeatedly washed with methanol followed by diethyl ether. It was then dried in vacuo. (yield : 80%) (e) [Cu(pn)(ox)]n, 57 A solution of pn (0.48ml, 3mM) in methanol was added dropwise to a suspension of copper(II) oxalate (0.30g, 1mM) in methanol with constant stirring for about 1 h. A clear dark blue

320

Chapter 7

solution was obtained from which solid light blue complex was found to be separating out soon making the supernatent liquid colourless. The solid complex was filtered and repeatedly washed with methanol followed by acetone. This was dried in vacuo. (yield : 80%)

7.3

Results and Discussion

7.3.1 Metal oxalates of Ni(II), Co(II) and Cu(II) Like succinic acid and malonic acid, oxalic acid also forms complexes with metals like Ni(II), Co(II) and Cu(II). The preparative procedures employed for generating these metal oxalates were almost same as that used for metal succinates and metal malonates which are described in chapters 3 and 5 respectively. The analytical data show a strict 1:1 complex (metal : ox) for all the oxalate complexes of the divalent metal ions. (Table 7.1). The compositions of various metal(II) oxalates were found to be [M(H2O)2(ox)]n for Ni(II) and Co(II) and [Cu(ox)]n for the Cu(II) ion. TG analysis could confirm the extent of water present in the complexes. The typical carboxylate peaks as(CO2)and s(CO2) for the oxalic acid are seen to occur at 1701 and 1443 cm-1 respectively. For the present metal oxalates these two peaks are seen to occur at 1636, 1362 cm-1 for [Ni((H2O)2(ox)]n (40), 1635, 1370 cm-1 for [Co(H2O)2(ox)]n (41) and 1649, 1364 cm-1 for [Cu(ox)]n (42) (Table 7.2). The greater difference in of these two bands compared to (258 cm-1) of oxalic acid indicates the bis-bidentate bridging character of the oxalate group.(7,32-38) The C-O stretching frequencies in these complexes are seen to occur in the range 1316-1321 cm-1 which is typical of chelating/bridging carboxylate group. Broad peaks in the range 3235-3250 cm-1 were seen in all the complexes (except for 42)

Interaction of Lewis-bases with Polymeric Metal Oxalates

321

which are characteristic of (O-H) band, indicating the presence of coordinated water in the system. It is interesting to note that is consistent with Irving-William series. Table 7.1 Elemental analytical data of metal(II) oxalates
Compound (Emp. formula) [Ni(H2O)2(ox)]n (NiC2H4O6) [Co(H2O)2(ox)]n (CoC2H4O6) [Cu(ox)]n (CuC2O4) Formula weight Elemental content(%) obsvd (calcd) C H 2.25 (2.21) 2.22 (2.20) M 32.2 (32.1) 32.3 (32.2) 42.0 (41.9) Green Colour

40 41 42

182.69

13.17 (13.14) 13.15 (13.12) 15.80 (15.84)

182.93

Rose

151.54

Blue

Table 7.2 Important IR spectral data of metal(II) oxalates (cm-1)

Compound H2ox (O-H) 3462 3250 3235 as(CO2) 1701 1636 1635 1649 S(CO2) 1443 1362 1370 1364 (C-O) 1330 1316 1321 1319

258 274 265 285

(O-H) 1625 1608 1610 -

40 41 42

The electronic spectra of various metal(II) oxalates were recorded in the solid state only because of the high insolubility of the complexes. The absorption values are given in Table 7.3. Nickel(II) oxalate (40) gave three peaks at 25310, 15600 and 10,650

322

Chapter 7

cm-1 which are typical of octahedral Ni(II).(39,40) and 14490 cm-1 which are

In the case of

cobalt(II) oxalate (41), the absorption peaks were seen at 18450 characteristic of octahedral Co(II) square planar species.(41,42) The broad absorption band was observed for copper(II) oxalate (42) at 13850 cm-1 which is expected for Cu(II) species.(43-45) Table 7.3 Electronic spectral and magnetic data of metal(II) oxalates
Compound Absor. Max (cm-1) 25310 15600 10650 18450 14490
3A 3A 3A

Assignments
2g(F)

eff (BM)

[Ni(H2O)2(ox)]n

3T1g(P) 3 3T1g(F) 2 3T2g(F) 1 2.92

40

2g(F) 2g(F)

[Co(H2O)2(ox)]n

T1g 4T1g(P)
4T 1g

41
[Cu(ox)]n

4A2g

4.57

42

13850

2B

1g

2A1g

1.43

Magnetic measurements showed that all the above oxalate complexes are paramagnetic in nature. The eff value of nickel(II) oxalate complexes was found to be 2.92 BM indicating that the complex is octahedral. The room temperature eff value of cobalt(II) oxalate was seen to be 4.57 BM which is characteristic of octahedral Co(II) species. The magnetic moment of copper oxalate complex was found to be 1.43 BM which is noticeably lower than the value expected of typical Cu(II) complexes. Both spectral and magnetic data indicated the strict six-coordinated character for

Interaction of Lewis-bases with Polymeric Metal Oxalates

323

Ni(II) and Co(II) complexes while four coordinated character for Cu(II) complex. A comparatively low value of eff for 42 indicates the close proximity of Cu ions in it for a possible Cu-Cu interaction. Based on the above observations and high insolubility the overall structure of the metal(II)oxalate complexes could be considered as polymeric in nature. 7.3.2 Interaction of Lewis-bases with polymeric nickel(II) oxalate The set of Lewis-bases chosen for interaction and

depolymerisation of nickel(II) oxalate were same as those used for the succinate and malonate systems. We have carried out the interaction of the bases with the metal oxalates under various reaction conditions and stoichiometric proportions as earlier. To isolate the new structural species, also we have employed some optimum reaction conditions. These along with some salient features of the reaction and the nature of products isolated are presented in Table 7.4. Unlike in the earlier cases the various Lewis-bases do not seem to depolymerise the metal oxalates very easily. Only pn seems to fragment the polymer skeleton as evident from the dissolution observed. All the isolated complexes showed 1:1 (nickel oxalate: Lewis-base) composition except for py adduct on elemental analysis (Table 7.5). The py adducts isolated in this system are seen to have 1:2 composition.

324

Chapter 7

Table 7.4 Interaction of metal oxalates with various Lewis-bases (LB)

Metal oxalate + LB (in MeOH) 40 + en (1:1) 40 + en (1:2) 40 + en (1:3) 40 + bipy (1:1) 40 + bipy (1:2) 40 + bipy (1:3) 40 + phen (1:1) 40 + phen (1:2) 40 + phen (1:3) 40 + py (1:1) 40 + py (1:2) Products Separated no stoichiometric compound no characterisable product [Ni(en)ox]n (43)

Conditions

Observation

stirring, RT, (2h) stirring, RT, (2h)

no observable change slight colour change from green to roseviolet colour change from green to rose violet (solution colourless) no observable change slight colour change from green to light violet colour change from green to light violet (solution colourless) no observable change slight colour change from green to light violet. (incomplete reaction) colour change from green to light violet (solution colourless) no observable change slight colour change from green to light green

stirring, RT, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h)

no stoichiometric compound no stoichiometric compound [Ni(bipy)ox]n (44)

no characterisable product no stoichiometric compound [(Ni(phen) (ox)).2H2O]n

(45)

no characterisable product no stoichiometric compound

40 + py (excess)

stirring under reflux, (2h)

colour change from green to light green (solution colourless)

[Ni(py)2ox]n

(46)

Interaction of Lewis-bases with Polymeric Metal Oxalates

40 + pn (1:1) 40 + pn (1:2) 40 + pn (1:3) 41 + en (1:1) 41 + en (1:2) 41 + en (1:3) 41 + bipy (1:1) 41 + bipy (1:2) 41 + bipy (1:3) 41 + phen (1:1) 41 + phen (1:2) 41 + phen (1:3) 41 + py (1:1) 41+ py (1:2) 41 + py (excess) 41 + pn (1:1) 41 + pn (1:2) 41 + pn (1:3) no characterisable product no characterisable product

325

stirring, RT, (2h) stirring, RT, (2h) stirring, RT, (2h) stirring, RT, (2h) stirring, RT, (2h) stirring, RT, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (1h) stirring under reflux, (2h) stirring, RT, (2h) stirring, RT, (2h) stirring, RT, (2h)

no observable change partial dissolution (blue solution) complete dissolution followed by blue solid separation no observable change slight colour change from rose to brown colour change from green to brown (solution colourless) no observable change slight colour change from rose to orange colour change from rose to orange (solution colourless) no observable change slight colour change from rose to orange colour change from rose to orange (solution colourless) no observable change light colour change from rose to pink colour change from rose to light pink (solution colour less) no observable change slight colour change from rose to pink colour change from rose to dark pink (solution colour less)

[(Ni(pn)(ox)).H2O]n (47) no characterisable product no stoichiometric compound [(Co(en)(ox)).H2O]n (48) no characterisable product no stoichiometric compound [Co(bipy)ox]n no characterisable product no stoichiometric compound [(Co(phen)(ox)).H2O]n (50) no characterisable product no stoichiometric compound [Co(py)2(ox)]n no characterisable product no stoichiometric compound [Co(pn)(ox)]n (52) (51) (49)

326

Chapter 7

42 + en (1:1) 42 + en (1:2) 42 + en (1:3) 42 + bipy (1:1) 42 + bipy (1:2) 42 + bipy (1:3) 42 + phen (1:1) 42 + phen (1:2) 42 + phen (1:3) 42 + py (1:1) 42 + py (1:2) 42 + py (excess) 42 + pn (1:1) 42 + pn (1:2) 42 + pn (1:3)

stirring, RT, (2h)

no observable change slight colour change from blue to violet colour change from blue to violet (solution colour less) no observable change slight colour change from blue to light blue colour change from blue to light blue (solution colour less) no observable change slight colour change from blue to light blue colour change from blue to light blue (solution colour less) no observable change slight colour change from blue to light blue colour change from blue to light blue (solution colour less) no observable change slight colour change from blue to light blue complete dissolution followed by light blue solid separation

no stoichiometric compound no characterisable product [(Cu(en)(ox)).2H2O]n no stoichiometric compound no characterisable product [Cu(bipy)(ox)]n no stoichiometric compound no characterisable product [Cu(phen)(ox)]n no stoichiometric compound no characterisable product [Cu(py)2(ox)]n (56) (55) (54)

stirring, RT, (2h)

stirring, RT, (1h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring under reflux, (2h) stirring, RT, (2h) stirring, RT, (2h) stirring, RT, (2h)

(53)

no stoichiometric compound no characterisable product [Cu(pn)(ox)]n (57)

Interaction of Lewis-bases with Polymeric Metal Oxalates

327

Table 7.5

Elemental analytical data of Lewis-base adducts of metal(II) oxalates

Elemental content % obsvd (calcd) C 23.20 (23.22) 47.57 (47.54) 44.15 (44.10) 47.20 (47.23) H 3.92 (3.90) 2.70 (2.66) 3.72 (3.70) N 13.55 (13.54) 9.20 (9,24) 7.34 (7.35) M 28.4 (28.3) 19.4 (19.3) 15.5 (15.4) Rose violet Light violet Light violet

Complex (Emp. formula) [Ni(en)(ox)]n NiC4H8N2O4 (43) [Ni(bipy)(ox)]n NiC12H8N2O4 (44) [(Ni(phen)(ox)).2H2O]n NiC14H14N2O7 (45) [Ni(py)2(ox)]n NiC12H10N2O4 (46) [(Ni(pn)(ox)).H2O]n NiC5H12N2O5 (47) [(Co(en)(ox)).H2O]n CoC4H10N2O5 (48) [Co(bipy)(ox)]n CoC12H12N2O4 (49) [(Co(phen)(ox)).H2O]n CoC14H12N2O6 (50) [Co(py)2(ox)]n CoC12H10N2O4 (51)

Formula Weight

Colour

206.69

302.88

380.92

304.89

3.28 (3.30)

9.20 (9.18)

19.3 (19.2)

Light green

238.82

25.10 (25.12) 21.30 (21.33) 47.52 (47.50) 46.28 (46.26) 47.20 (47.19)

5.10 (5.06) 4.50 (4.48) 2.68 (2.66) 3.35 (3.33) 3.31 (3.30)

11.70 (11.72) 12.40 (12.44) 9.25 (9.23) 7.70 (7.71) 9.20 (9.17)

24.6 (24.5) 26.2 (26.1) 19.5 (19.4) 16.3 (16.2) 19.2 (19.3)

Blue

224.93

Brown

303.12

Orange

363.16

Orange

305.13

Light pink

328

Chapter 7

[Co(pn)(ox)]n CoC5H10N2O4 (52) [(Cu(en)(ox)).2H2O]n CuC4H12N2O6 (53) [Cu(bipy)(ox)]n CuC12H8N2O4 (54) [Cu(phen)(ox)]n CuC14H10N2O5 (55) [Cu(py)2(ox)]n CuC12H10N2O4 (56) [Cu(pn)(ox)]n CuC5H10N2O4 (57)

221.06

27.18 (27.14)

4.50 (4.55)

12.70 (12.66)

26.7 (26.6)

Dark pink

247.54

19.40 (19.39)

4.85 (4.88)

33.15 (33.12)

25.7 (25.6)

Violet

307.73

46.82 (46.79) 48.06 (48.03) 46.51 (46.49) 26.60 (26.58)

2.65 (2.62) 2.90 (2.88) 3.20 (3.25) 4.50 (4.46)

9.12 (9.09) 8.02 (8.00) 9.05 (9.03) 12.42 (12.40)

20.7 (20.6) 18.2 (18.1) 20.6 (20.5) 28.2 (28.1)

Light blue Light blue Light blue Light blue

349.77

309.74

225.67

7.3.3

IR spectra of Lewisbase adducts of nickel(II) oxalate As compared to the IR spectrum of nickel(II) oxalate, its

Lewis-base adducts gave several additional and modified peaks. The as(CO2) band occurring at 1636 cm-1 in [Ni(H2O)2(ox])n (40) were found shifted to 1547-1621 cm-1 in its adducts and the s(CO2) band observed at 1362 cm-1 was found lowered to 1335-1380 cm-1 in its adducts. The individual details are discussed below and important frequencies are given in Table 7.6. In the IR spectrum of the adduct [Ni(en)(ox)]n, 43, the as(NH2) and s(NH2) bands were observed at 3283 and 3158 cm-1 respectively. The bending mode (NH2) was seen at 1620 cm-1. A sharp band observed at 1023 cm-1 could be assigned to (C-N) stretching of

Interaction of Lewis-bases with Polymeric Metal Oxalates

329

en. The as(CO2) and s(CO2) bands were observed at 1547 and 1335 cm-1 respectively. The values suggest the bridging character of COO- group of oxalate moiety in it. Table 7.6 IR spectral data of nickel(II) oxalate and its various Lewisbase adducts (cm-1)
Adducts (O-H) as(CO2) s(CO2) 40 3250 1636 1362 274 1316 43 1547 1335 212 1302 44 1602 1352 250 1317 1633 45 3390 1580 1345 235 1282 1646 1621 1363 258 1315 1605 46 47 3450 1590 1380 210 1313 -

(C-O)

C C

C N
(C-N) (C-H) (C-H) (NH2) (NH2) (NH2) wag M-N stret Ring deformation (outplane) (inplane)

1023 3283 3158 1620 751 526

1475 771 1022 -

1421 725 -

1480 -

1018 3310 3280 1610 799 470

498 653

480 639

445 660

330

Chapter 7

For the adduct [Ni(bipy)(ox)]n, 44, new peaks were observed at 771, 1022, 1475 and 1633 cm-1 indicating that bipy is coordinated to Ni through both of its pyridyl nitrogen. The as(CO2) and s(CO2) bands of oxalate moiety were observed at 1602 and 1352 cm-1. The in-plane and out-of-plane ring deformation modes of bipy were observed to 653 and 499 cm-1 respectively. The IR spectrum of the complex [(Ni(phen)(ox)).2H2O]n, 45, gave new peaks at 725,1421 and 1646 cm-1 indicating the presence of phen. The bands at 1421 and 1646 cm-1 could be assigned to the ring skeletal vibration of phen. Its ring deformation modes were observed at 639 and 480 cm-1. The as(CO2) and s(CO2) bands of oxalate group were seen shifted to 1580 and 1345 cm-1 respectively and the apperance of a broad band at 3390 cm-1 indicates the presence of lattice water in it. For the adduct [Ni(py)2(ox)]n, 46, all the characteristic peaks of pyridine were observed in addition to the peaks due to parent oxalate. The ring skeletal bands of pyridine were observed at 1605 and 1480 cm-1. The as(CO2) and s(CO2) bands of oxalate moiety were observed at 1621 and 1363 cm-1 respectively. The ring deformation modes of pyridine were observed at 660 and 445 cm-1 . The IR spectrum of the adduct [(Ni(pn)(ox)).H2O]n, 47, gave peaks at 3313 and 3278 cm-1 which are characteristic of as(NH2) and s(NH2) vibrations of coordinated pn. The (NH2) band was observed at 1610 cm-1 and (C-N) band was seen at 1018 cm-1. The as(CO2) and s(CO2) bands of oxalate moiety were observed at 1590 and 1380 cm-1 respectively. The appearance of a broad band at 3450 cm-1 indicates the presence of lattice water in it.

Interaction of Lewis-bases with Polymeric Metal Oxalates

331

As in the case of succinates and malonates we have made attempts to look at the gradation of in the nickel(II) oxalate and its adducts also. While in parent nickel(II) oxalate the progressively in the order is 274 cm-1, in its adducts the difference is seen to be decreasing 40 > 46 > 44 > 45 > 43 > 47. This is consistent with the fact that pn and en are totally -donors (with no -accepting character) while phen, bipy and py have both donor and -accepting nature. The -donor ligands would enhance the electron density on the metal which would in turn make the metal release more electron to the * orbitals of the oxalate moiety. The effect of such back donation would be to decrease the O-C-C-O bond order in the oxalate which gets reflected in also. In the case of phen, bipy and py the Lewis-bases have on their own some

-acceptor property also and hence will not try to accumulate

much electron density on the metal. Consequently the back donation to oxalate * orbital would be less. The trend observed agrees well with the expectation. 7.3.4 Electronic spectra and magnetic data of Lewis-base adducts of nickel(II) oxalate The electronic spectra of various adducts of nickel(II) oxalate isolated were recorded in solid state. Some of the spectra are reproduced in Fig.7.1. The characteristic special features in the bands of parent nickel(II) oxalate are seen disappearing and new set of absorptions are seen emerging in its adducts. The absorption bands were observed in the region 25910-27620 cm-1, 1626018380 cm-1 and 10730-11670 cm-1 in all the adducts. These bands could be assigned to 3A2g(F) 3T1g(P) (3); 3A2g(F) 3T1g(F) (2) and
3A (F) 2g

3T2g(F) (1) respectively in agreement with typical Ni(II)

332

Chapter 7

octahedral

complex.(39,40)

We

have

evaluated

the

ligand-field

parameters Dq, for the various adducts employing the methods as discussed earlier (Chapter 3). 47. The Dq values among the various adducts were seen to decrease in the order 43 > 46 > 44 > 45 > The trend is seen to be more or less dependent on the pka value of the various Lewis-bases. Eventhough the pKa value of pn is greater than that of en, the Dq value of pn adduct (47) is found to be less than that of en adduct (43). This may be because of the relatively less chelating stability of pn as compared to en. The eff values evaluated for all the Ni(II) adducts are found to be in the range 3.01-3.18 BM which are in agreement with the values expected for octahedral complexes. The electronic transitions, their assignments and magnetic moment data are given in Table 7.7.

Interaction of Lewis-bases with Polymeric Metal Oxalates

333

(a) [Ni(H2O)2(ox)]n, 40 (b) [Ni(en)(ox)]n, 43 (c) [Ni(bipy)(ox)]n, 44 (d) [(Ni(phen)(ox)).2H2O]n, 45 (e) [Ni(py)2(ox)]n, 46

(f) [(Ni(pn)(ox)).H2O]n, 47

Fig. 7.1

Electronic spectra of Lewis-base adducts of nickel(II) oxalate

334

Chapter 7

Table 7.7 Electronic spectral and magnetic moment data of Lewisbase adducts of nickel(II) oxalate
Complex Absor. max (cm-1) 25310 40 15600 10650 27620 43 18380 11670 26110 44 17850 10950 25910 45 17950 10800 26250 46 16260 11130 26040 47 16610 10730 Assignment s* 3 2 1 3 2 1 3 2 1 3 2 1 3 2 1 3 2 1
3A (F) 2g

Dq (cm-1)

B (cm-1)

2/1

eff (BM)

1065

0.60

597

1.46

2.92

1167

0.65

773

1.57

3.07

1095

0.63

741

1.63

3.15

1080

0.64

764

1.66

3.18

1113

0.61

608

1.47

3.01

1073

0.66

697

1.55

3.05

*3A2g(F) 3T2g(F) (1);

3T1g(F) (2);

3A 2g

3T1g(P) (3)

Interaction of Lewis-bases with Polymeric Metal Oxalates

335

7.3.5 Interaction of Lewis-bases with polymeric cobalt(II) oxalates Like nickel(II) oxalate, cobalt(II) oxalate also can be expected to have an extended polymeric structure as mentioned in section 7.3.1 based on its spectral properties. The set of Lewis-bases chosen for the adduct formation with the cobalt(II) oxalate were same as those used for nickel(II) oxalate. Interaction with various Lewis-bases was carried out in different reaction conditions as before. The details are presented in Table 7.4. We could not find any indication of depolymerisation being initiated as none of the Lewis-bases tend to bring the metal oxalate in solution. The analytical data shown in Table. 7.5 confirm the 1:1 composition (cobalt oxalate : Lewis-base) for all the adducts except with pyridine. The pyridine adduct, however, has 1:2 composition. 7.3.6 IR spectra of Lewis-base adducts of cobalt(II) oxalate The presence of Lewis-bases in all the adducts could be confirmed by their characteristic peaks in the IR spectra. The peaks due to oxalate moiety were also present with some shift in their position as compared to the values in the parent metal oxalates. The asymmetric stretching as(CO2) band observed at 1635 cm-1 in parent cobalt(II) oxalate was found shifted to 1600-1622 cm-1 in its adducts. Similarly the s(CO2) band observed at 1370 cm-1 discussed below in detail. In the IR spectrum of [(Co(en)(ox)).H2O]n, 48, the as(NH2) and s(NH2) band were seen at 3340 and 3204 cm-1 showing the coordination of en. The as(CO2) and s(CO2) bands of the oxalate group are observed in the adduct at 1600 and 1365 cm-1 respectively. The (NH2) and (C-N) bands of en were seen at 1630 and 1061 cm-1 was found shifted to 1350-1388 cm-1 in them. The spectra of individual adducts are

336

Chapter 7

respectively and the appearance of a broad band at 3440 cm-1 indicates the presence of lattice water in it. In the case of [Co(bipy)(ox)]n adduct, 49, new peaks were observed at 771, 1013, 1455 and 1674 cm-1 indicating that bipy is coordinated to Co through both of its pyridyl Ns. The C-H out-of-plane skeletal vibration of bipy (C-H) at 771 cm-1 gets split into 798 and 737 cm-1 in the adduct indicating the bidentate nature of 2,2'-bipyridyl. The ring deformation modes of bipy moiety were seen at 660 and 488 cm-1 in the adduct. The peaks at 1607 and 1355 cm-1 could be assigned to the asymmetric and symmetric stretching bands of the COO- group of oxalate moiety in the adduct. The spectrum of [(Co(phen)(ox)).H2O]n, 50, showed new bands at 730, 1425 and 1640 cm-1 showing the chelating nature of phen. The as(CO2) and s(CO2) bands of the oxalate group were seen at 1605 and 1350 cm-1 respectively. The ring deformation modes of phen moiety appear at 643 and 428 cm-1 respectively. The presence of lattice water is confirmed by the appearance of a broad band at 3407 cm-1. In the case of [Co(py)2(ox)]n adduct, 51, new peaks were to (C-C) and (C-N) ring 1622 and 1361 cm-1 pyridine. The as(CO2) and s(CO2) observed at 1610 and 1478 cm-1 due stretching skeletal vibrations of

peaks of oxalate group were seen shifted to

respectively. The in-plane and out-of-plane ring deformation modes of pyridine moiety were observed at 632 and 492 cm-1. In the pn adduct, [Co(pn)(ox)]n, 52, peaks at 3360 and

3240 cm-1 characteristic of NH2 stretching of coordinated pn are seen. The bands at 1654 and 1048 cm-1 could be assigned as (NH2) and (C-N) vibrations of pn. The as(CO2) and s(CO2) bands of COO group of oxalate moiety were observed at 1601 and 1388 cm-1

Interaction of Lewis-bases with Polymeric Metal Oxalates

337

respectively.

All the other important IR absorption frequencies of

cobalt(II) oxalate and its Lewis-base adducts are given in Table 7.9. The

found

for

the

adducts

are

in

the

order

41 > 51 > 50 > 49 > 48 > 52 which is in the expected order when we consider the -donor ability of pn and en and -donor and

-acceptor property of phen, bipy and py.

Table 7.9 IR spectral data of Lewis-base adducts of cobalt(II) oxalate (cm-1)
Adducts (O-H) as(CO2) s(CO2) 41 3235 1635 1370 265 1321 48 3440 1600 1365 235 1317 1061 3290 3204 1630 778 575 49 1607 1355 252 1310 1674 1455 771 1013 50 3407 1605 1350 255 1312 1640 1425 730 51 1622 1361 261 1315 1610 1478 52 1601 1388 213 1304 1048 3310 3240 1654 767 551

(C-O)

C C

C N
(C-N) (C-H) (C-H) (NH2) (NH2) (NH2) wag M-N stret Ring deformation (outplane) (inplane)

488 660

481 643

492 632

338

Chapter 7

7.3.7 Electronic spectra and magnetic data of Lewis-base adducts of cobalt(II) oxalate The electronic spectra of all the adducts of cobalt(II) oxalate were recorded in solid-state because of their insolubility. Some of the spectra are reproduced in Fig. 7.2. All the adducts show the set of bands in the region 15480-15870 and 19530-21550 cm-1. These are very characteristic of octahedral Co(II) and could be assigned to 4T1g4A2g and 4T1g4T1g(P) transitions respectively.(41,42) The data are tabulated in Table 7.10. Table 7.10 Electronic spectral and magnetic data of Lewis-base adducts of cobalt(II) oxalate
Absor. max (cm-1) 18450 14490 21550 15870 21010 15580 21270 15530 19530 15480 21320 15600 Assignments
4T 1g

Adducts

eff (BM) 4.57

41

4T1g(P) 4A2g

4T 1g 4T 1g

48

4T1g(P) 4A2g

4T 1g 4T 1g

4.71

49

4T1g(P) 4A2g

4T 1g 4T 1g

4.74

50

4T1g(P) 4A2g

4T 1g 4T 1g

4.77

51

4T1g(P) 4A2g

4T 1g 4T 1g

4.65

52

4T1g(P) 4A2g

4T 1g

4.69

Interaction of Lewis-bases with Polymeric Metal Oxalates

339

Fig.7.2 . Electronic spectra of cobalt(II) oxalate and its Lewis-base adducts (a) (b) (c) [Co(H2O)2(ox)]n, 41 [(Co(en)(ox)).H2O]n, 48 [Co(bipy)(ox)]n, 49 (d) (e) (f) [(Co(phen)(ox)).H2O]n, 50 [Co(py)2(ox)]n, 51 [Co(pn)(ox)]n, 52

340

Chapter 7

The room temperature magnetic susceptibility measurements were carried out and eff values evaluated for all the adducts. These were found to be in the range 4.65-4.77 BM. No definite trend in eff values could be seen among these adducts. The high spin rather than low spin state manifested in the eff values for all the Lewis-base adducts indicate the weak ligation property of the Lewis-bases with the parent cobalt(II) oxalate. 7.3.8 Interaction of Lewis-bases with copper(II) oxalate Just as in the case of nickel(II) and cobalt(II) oxalates, adduct formation studies were investigated with polymeric copper(II)oxalate also with the same set of ligands. The interaction was studied in various reaction conditions and also by changing the stoichiometric ratio of the parent oxalate and Lewis-bases. These along with some salient features of the reactions and products isolated are presented in Table 7.4. The analytical data shown in Table 7.5 confirm the 1:1 composition (metal oxalate: Lewis-base) for all the Lewis-base adducts isolated except that with pyridine. 7.3.9 IR spectra of Lewis-base adducts of copper(II) oxalate Like in the case of nickel(II) and cobalt(II) oxalate, copper(II) oxalate and its Lewis-base adducts also show characteristic peaks in their infrared spectra. The as(CO2) observed at 1649 cm-1 in parent copper(II) oxalate was found shifted to 1580-1624 cm-1 in its adducts and the s(CO2) band observed at 1364 cm-1 to 1345-1390 cm-1 in them. The individual details are discussed below. In the IR spectrum of [(Cu(en)(ox)).2H2O]n, 53, new bands were observed at 3306 and 3219 cm-1 which could be assigned as as(NH2) and s(NH2) vibrations respectively. The (NH2) band was seen at 1590 cm-1 and the (C-N) band was observed at 1044 cm-1. The as(CO2) and

Interaction of Lewis-bases with Polymeric Metal Oxalates

341

s(CO2) bands of COO group of oxalate moiety were observed at 1596 and 1390 cm-1 respectively. The presence of lattice water is indicated by the appearance of a broad band at 3390 cm-1. For the adduct [Cu(bipy)(ox)]n, 54, new bands were observed at 775, 1019, 1472 and 1661 cm-1 indicating that bipy is coordinated to Cu through both of its pyridyl N. The C-H out-of plane skeletal vibration of bipy (C-H) at 775 cm-1 gets split into 782 and 731 cm-1 in the adduct. This reflects the bidentate nature of 2,2'-bipyridyl. Moreover as(CO2) and s(CO2) bands of oxalate moiety were seen shifted to 1597 and 1360 cm-1. The ring deformation modes of bipy appear at 662 and 486 cm-1 respectively. In the IR spectrum of [Cu(phen)(ox)]n, 55, new peaks were seen at 723, 1427 and 1663 cm-1 showing that phen is coordinated through both of its pyridyl N. The as(CO2) and s(CO2) bands of oxalate moiety were observed at 1603 and 1345 cm-1. The ring deformation modes of phen moiety appear at 646 and 482 cm-1 respectively. For the adduct [Cu(py)2(ox)]n, 56, new bands are seen at 1600 and 1487 cm-1 which could be assigned to (C-C) and (C-N) ring stretching skeletal bands of pyridine. The peaks at 1624 and 1362 cm-1 are due to as(CO2) and s(CO2) modes of COO group of oxalate moiety. The ring deformation modes of pyridine moiety were observed at 687 and 443 cm-1 respectively. In the IR spectrum of the adduct [Cu(pn)(ox)]n, 57, the as(NH2) and s(NH2) vibrations of coordinated pn were observed at 3290 and 3250 cm-1. The as(CO2) and s(CO2) bands of oxalate moiety were observed at 1580 and 1378 cm-1 respectively. All other relevant IR

342

Chapter 7

absorption frequencies of copper(II) oxalate and its Lewis-base adducts are shown in Table 7.11. In the system also we have monitored the trend in among the various adducts. The order was found to be 42 > 56 > 55 > 54 > 53 > 57. Table 7.11 IR spectral data of Lewis-base adducts of copper(II) oxalate (cm-1)
Adducts (O-H) as(CO2) s(CO2) 42 1649 1364 285 1319 53 3390 1596 1390 206 1310 1044 3306 3219 1590 714 525 54 1597 1360 237 1294 1661 1472 775 1019 55 1603 1345 258 1298 1663 1427 723 56 1624 1362 262 1316 1600 1487 57 1580 1378 202 1269 1038 3290 3250 1626 785 498

(C-O)

C C

C N
(C-N) (C-H)
(C-H)

(NH2) (NH2) (NH2) wag (M-N)stret Ring deformation (outplane) (inplane)

486 662

482 646

443 686

Interaction of Lewis-bases with Polymeric Metal Oxalates

343

7.3.10

Electronic spectra and magnetic data of Lewis-base adducts of copper(II) oxalate

The electronic spectra of various adducts of copper(II) oxalate were recorded in solid state. Some of these are reproduced in Fig.7.3. The data are presented in Table 7.12. The authenticity of all the peaks was confirmed by recording the spectrum by repeated sample preparation. In all the adducts generated in the present study a broad band occur in the region 14180-18650 cm-1. This is indicative of tetragonal configuration around copper(II) ion.(46,47) Moreover both n* and * bands were found to be blue shifted and appearing in the region 3330-33670 cm-1 and 40160-41150 cm-1 respectively, compared to that of the parent complex. Further, the electronic spectra of all the complexes exhibit an intense absorption band in the region 26450-28980 cm-1 which could be assigned due to charge transfer transitions.

344

Chapter 7

Table 7.12 Electronic spectral data and magnetic moments of Lewisbase adducts of copper(II) oxalate
Adducts Absorption max

(cm-1)

Assignments * n* Charge Transfer 2B 2 1g A1g * n* Charge Transfer 2B 2 1g A1g * n* Charge Transfer 2B 2 1g A1g * n* Charge Transfer 2B 2 1g A1g * n* Charge Transfer 2B 2 1g A1g * n* Charge Transfer 2B 2 1g A1g

eff (BM) 1.43

42

53

54

55

56

40000 33220 26040 13850 40160 33330 28980 18650 40480 33670 28090 14490 41150 33440 27700 14180 40320 33550 26450 15190 40810 33330 28190 15870

1.62

1.67

1.68

1.57

57

1.59

Interaction of Lewis-bases with Polymeric Metal Oxalates

345

(a) [Cu(ox)]n, 42 (b) [(Cu(en)(ox)).2H2O]n, 53 (c) [Cu(bipy)(ox)]n, 54 (d) [Cu(phen)(ox)]n, 55 (e) [Cu(py)2(ox)]n, 56

(f) [Cu(pn)(ox)]n, 57

Fig.7.3

Electronic spectra of Lewis-base adducts of copper(II) oxalate.

The magnetic moment values of the present copper(II) complexes vary in the range 1.57-1.68 BM (Table 7.12). comparatively The lower magnetic moment values seen for all these

polymeric adducts indicates the possibility of structures with close Cu-Cu proximity.(48)

346

Chapter 7

7.3.11

EPR spectra of Lewis-base adducts of copper(II) oxalate

Compared to the adducts of copper(II) succinate and copper(II) malonate, the adducts of copper(II) oxalate are insoluble in most of the solvents. Their polymeric nature is also evident from the electronic and IR spectral data. Owing to this, the EPR spectra of this compounds could be recorded in solid state only at room temperature. Fig 7.4 gives the spectra of en adduct 53, bipy adduct 54, py adduct 56 and pn adduct 57. Eventhough the spectra were not well resolved, their features appear almost the same in all the cases. Comparing with some of the known spectra, the g and g values for this adducts could be evaluated. These are given in Table 7.13. The trend g>g>2.0023 seen in all the adducts indicate dx2-y2 ground state in them.(49) The parameters giso and G could be calculated for the adducts by using the equations mentioned earlier. The axial symmetry parameter, G, which indicate the nature of exchange interaction between the copper centres for the adducts has value below 4.(50) Significant exchange interaction can therefore be expected from all these adducts. The nature of the EPR spectra of the pn adduct 57 and its G value (1.60) indicate that the structural features of 57 could be much different from those of others.

Interaction of Lewis-bases with Polymeric Metal Oxalates

347

(a) [(Cu(en)(ox)).2H2O]n, 53 (b) [Cu(bipy)(ox)]n, 54 (c) [Cu(py)2(ox)]n, 56

(d) [Cu(pn)(ox)]n, 57

Fig. 7.5 The EPR spectra of the polymeric adducts of copper(II) oxalate.

Table 7.13 The various EPR parameters of the polymeric adducts of copper(II) oxalate Adducts 53 54 56 57 g 2.18 2.21 2.16 2.14 g 2.06 2.08 2.07 2.09 giso 2.10 2.12 2.10 2.11 G 3.00 2.63 2.29 1.60

348

Chapter 7

All

the

analytical,

spectral

(IR,

electronic, EPR), and

magnetic moment data of the adducts of metal(II) oxalate clearly indicate that all of them have a polymeric octahedral structure with bis-bidentate chelating oxalate functions. The high insoluble nature of all the adducts in various organic solvents also gave a clear evidence for their polymeric structure. References 1. (a) C. Sterling, Nature; 205 (1965) 588 (b) C. Sterling, Science; 146 (1964) 518 (c) O. C. Pluchery, J. C. Mutin, J. Bouillot and J. C. Niepce, Acta Crystallogr; C45 (1989) 1699 (d) I. L. Jenkins, F. H. Moore and M. J. Waterman, J. Inorg. Nucl. Chem; 27 (1965) 77 2. (a) R. P. Farrell, T. W. Hambley and P. A. Lay, Inorg.Chem; 34 (1995) 757 (b) L. Soto, J. Garcia. E. Escriva, J. P. Legors, J. P. Tuchagues, F. Dahan and A. Fuertes, Inorg. Chem; 28 (1989) 3378 (c) R. Pellaux, H. W. Schmalle, S. Decurtins, R. Huber, P. Fischer, B. Ouladdiaf, T. Hauss and S. Decurtins, Inorg. Chem; 36 (1997) 2301 3. (a) Y. H. Kiang, S. Lee, Z. Xu, W. Choe and G. B. Gardner, Adv. Mater; 12 (2000) 767 (b) G. B. Gardner, D. Venkataraman, J. S. Moore, S. Lee, Nature; 374 (1995) 792 4. 5. R. B. English and D. J. Eve, Inorg. Chim. Acta; 203 (1993) 219 E. E. Baeva, Y. N. Mikhailov, Y. E. Gorbunova, L. B. Serezhkina and V. N. Serezhkin, Russ. J. Inorg. Chem; 48 (2003) 1651

Interaction of Lewis-bases with Polymeric Metal Oxalates

349

6.

(a) E. Jeanneau, N. Audebrand and D. Louer, Chem. Mater; 14 (2002) 1187 (b) E. Jeanneaue, N. Audebrand, J. P. Auffredic and D. Louer, J. Mater. Chem; 11 (2001) 2545 (c) C. Boudaren, J. P. Auffredic, D. Louer and M. Louer, Chem. Mater; 12 (2000) 2324 (d) E. Jeanneau, N. Audebrand and D. Louer, J. Mater. Chem; 12 (2002) 2383

7.

H. Tamaki, Z. J. Zhong, N. Matsumoto, S. Kida, M. Koikawa, N. Achiwa, Y. Hashimoto and H. Okawa, J. Am. Chem. Soc; 114 (1992) 6974 O. Costisor, M. Julve, F. Lloret, Y. Journaux and W. Linert, Inorg. Chim. Acta; 324 (2001) 352 M. Delarco, S. Gutierrez, C. Martin and V. Rives, Inorg. Chem. 42 (2003) 4232 R. Pellaux, H. W. Schmalle, S. Decurtins, P. Fischer, F. Fauth, B. Ouladdiaf and T. Hauss, Physica B; 234 (1997) 783 M. C. Leon, E. Coronado, J. R. G. Mascaros and C. J. G. Garcia, Chem. Commun; (1997) 1727 S. G. Carling, C. Mathoniere, P. Day, K. M. A. Malik, S. J. Coles and M. B. Hursthouse, J. Chem. Soc. Dalton Trans; (1996) 1839 E. Coronado, J. R. G. Mascaros, C. J. G. Garcia and J. M. M. Agudo, Adv. Mater; 11 (1999) 558 S. Decurtins, H. W. Schmalle, H. R. Oswald and A. Linden, Inorg. Chim, Acta; 216 (1994) 65 C. J. Nuttall and P. Day, Chem. Mater; 10 (1998) 3050 E. Coronado, J. R. G. Mascaros, C. J. G. Garcia and J. M. M. Agudo, J. Chem, Soc. Dalton Trans; (2000) 3955

8. 9. 10. 11. 12.

13. 14. 15. 16.

350

Chapter 7

17. 18. 19.

X. F. Chen, P. Cheng, X. Liu, B. Zhao, D. Z. Liao, S. P. Yan and Z. H. Jiang, Inorg. Chem; 40 (2001) 2652 J. Y. Lu, M. A. Lawandy and J. Li, Inorg. Chem; 38 (1999) 2695 (a) P. Roman, A. Luque and J. I. Beitia, Polyhedron; 14 (1995) 2863 (b) O. Castillo, A. Luque and P. Roman, J. Mole. Struc; 570 (2001) 181

20.

(a) H. Oshio and N. Nagashima, Inorg. Chem; 31 (1992) 3292 (b) J. Foley, N. Ray, D. Sheahan and B. Hathaway, J. Chem Soc. Dalton Trans; (1982) 1117

21. 22. 23. 24. 25. 26. 27. 28. 29.

J. K. Tang, E. Q. Gao, W. M. Bu and G. L. Wang, J. Mole. Struc; 525 (2000) 271 O. Castillo, A. Luque and P. Roman, Inorg. Chem. Commun; 4 (2001) 640 H. Y. Shen, W. M. Bu, D. Z. Liao and S. P. Yan, Inorg. Chem; 39 (2000) 2239 D. Armentano, G. D. Munno, F. Lloret and M. Julve, Inorg. Chem; 41 (2002) 2007 T. Fujino, Y. Hoshino, S. Igarashi, Y. Masuda and Y. Yukawa, Inorg. Chim. Acta; 357 (2004) 11 D. J. Price, A. K. Powell and P. T. Wood, J. Chem. Soc. Dalton Trans; (2000) 3566 M. C. Munoz, M. Julve and J. Faus, J. Chem. Soc. Dalton Trans; (1998) 3125 D. J. Price, S. Tripp and A. K. Powell, Chem. Eur. J; 7 (2001) 200 F. Pointillart, C. Train, M. Gruselle, F. Villain, H. W. Schmalle and M. Verdaguer, Chem. Mater; 16 (2004) 832

Interaction of Lewis-bases with Polymeric Metal Oxalates

351

30. 31. 32. 33. 34. 35. 36. 37. 38. 39 40. 41. 42. 43. 44. 45.

P. Vitoria, I. Muga, A. Luque, L. Lezama and J. I. Beitia, Inorg. Chem; 42 (2003) 960 R. Murugesan and E. Subramanian, Bull. Mater. Sci; 25 (2002) 613 R. Cortes, M. K. Urtiaga, I. Lezama and T. Rojo, Inorg. Chem; 33 (1994) 829 K. Nakamoto, Infrared Spectra of Inorganic and Coordination Compounds, 2nd Ed, Wiley-Interscience, New York, (1970) 244 P. Roman, A. Luque, I. Beitia, J. Cano and M. Julve, Inorg. Chem; 35 (1996) 3741 M. Julve, M. Verdaguer, J. Faus and X. Solans, J. Chem. Soc. Dalton Trans; (1992) 3209 A. Bianchi, A. Corradi and M. Julve, Inorg. Chem; 27 (1988) 4174 N. F. Curtis, J. Chem. Soc; (1963) 4109 N. F. Curtis, J. Chem. Soc. A; (1968) 1584 R. S. Drago, Physical Methods in Chemistry Saunders, Philadelphia (1969). A. B. P. Lever Inorganic Electronic Spectroscopy. 2nd Ed, Elsevier, Amsterdam, (1984) A. B. P. Lever, Inorganic Electronic Spectroscopy 2nd Ed, Elsevier, Amsterdam, (1968) 534 K. Dey and D. Padhayay, Indian. J. Chem; 31A (1992) 34 R. H. Holm and M.J.O Connor, Prog. Inorg. Chem; 14 (1971) 241 F. A. Cotton and J. J. Wise, Inorg. Chem; 6 (1967) 917 G. Marcotrigiano, L. Menabue, G. C. Pellacani and M. Saladini, Inorg. Chim. Acta; 34 (1979) 43

352

Chapter 7

46. 47. 48. 49. 50.

Y. Nishida and S. Kida, Coord. Chem. Rev; 15 (1975) 279 M. A. Hitchman and T. D. Waite, Inorg.Chem; 15 (1976) 2150 M. R. G. Nair and C. P. Prabhakaran, J. Inorg. Nucl. Chem; 43 (1981) 3390 B. Singh, B. P. Yadava and R. C. Aggarwal, Indian J. Chem; 23 A (1984) 441 M. Shakir, S. Islam, A. K. Mohamed and N. Jahan, Trans. Met. Chem; 22 (1996) 189

Thermal Dissociation Features of

Oxalate Complexes of Ni(II), Co(II) and

Cu(I1) and their Lewis-base Adducts

occurs in a three-step process for M = Al, Cr, M n and Co a n d a twostep process for M
=

Fe. Reports are also available on the thermal

behaviour of the complexes with composition [M(E)z(ox)].2H2O[181 (M= M n , Co, Ni and Cu; L = 2,4'-bipy) in air and their decompositions are found to proceed in three-stage steps. Thermal

decomposition of metal oxalate complexes with hydrazine having the compositions, Cdz[~x)n .NzH+, Cd(ox). NzH4.0.5H20 and Cd(ox).1.5 N2H4
were also known.!lgl The mechanism and h e t t c s of thermal

decomposition of ammoniacal complex of copper(II),with composition

[Cu (NHs) ox) 1, has been studied in merent atmospheres such as air
and Nz. In nitrogen, it involves endothermic deammoniation
followed by decomposition to elemental copper, whereas i n air, oxidative decomposition makes the process complex and CuO is
obtained as the frnal product. Another significant observation made

was that

i n nitrogen

atmosphere, the

deammoniation and

decomposition have been found to be zero and first order I-espectively. Study on thermal spin transition in a mixed ligand comples with composition, [Co(L)3][LiCr(ox)3]~2{~~ (L = 2,2'-bipy),has
also been reported. As we expect varied thermal behaviour in the

metal oxalates compared to other dicarboxylate species we present,

a systematic investigation on the thermal behaviour of metal

oxalates and their various Lewis-base adducts and also present various thermodynamic parameters associated with them.

8.2

Results and Discussion

The thermal decomposition characteristics of six coordinated

complexes of Ni(II) and Co(II) and four coordinated complexes of

CulII) and their six coordinated Lewis-base adducts were s t u d e d i n

f i ~ r . m a r ~ s o ~ i a t iF oa a tm

of

O&te

C o m p h p offi(IaCooI} and Cu(-II) a d .

... .... 355

Thc

nitrogen

atmosphere, with a heating a

of lOoC/rnin.

phenomenological aspects, kinetic and thennodynamic parameters associated with the thermal reactions and trend in thermal behaviour
of vanous adducts of metal oxalates are d~scusscd below.

8.2.1 Phenomenological Aspects

8 . 2 . 1 . 1 Thermal decomposition of nickel(I1)oxalate i n Nz
The therrnogram of [Ni(HaO)~(ou)], is given i n Fig 8.1. This
compound is found to be thermally stable upta 1550C. The decomposition of the complex Is seen starting a t 1 5 5 C (T,) and
progressing till 3 100C (Tf) with a peak temp of 2 3 W C (T,). The mass

loss observed (19.60/u) was i n good agreement with the theoretical

value (19.71A)for the loss of two moles of coordmated water. The

second stage i s seen starting at 3 100C ( T i ) and ending at 3580C ( T i ) with a peak temp of 3570C (Ta). This could be attributed
to the

decomposition of [Ni(ox)],t o yield NiO as the find product. T h e loss

in mass corresponding to this decomposition

stage was 39.90%,

which is in good agreement with the theorehcal value of 39.41%

for

the loss o f some gaseous products. The mass of the residue observed
after t h complete ~ decomposition was fourld l o be 40.50% which is i n
close agreement with the theoretical value of 40.88%. The authenticity
of ~e final product NiC) was d s o confirmed by elemental analysis.

Fig 8.1 The thennogram (TG/DTG) 0f[Ni(&0)2(0~)]n

in Nz

The decomposition features are surnmarised below in Table 8.1.

Table 8.1. Thermal characteristics oJ(Ni(Hz0)2(ox&

Temp range (OC)

Compound

Peak temp
PC)

Wt. loss(O/~j
Stages

Found
1

CaIcd

Probable reaction
eq 8 . 1

155-310
(N i(H20)2(OX) In

230
357

19.60
39.90
40.50

19.71 39.4 1
40.88 Iresidue)

310-358
Above 358

I1

eq 8.2
NiO

(residue)

!N~(ox)n

A,NZ 310 - 358

(k

NiD

gaseous products

8.2.1.2 Lewis-base adducts of nickel(I1)oxalate

/Ni(e~ i )
43

From the thern~ogramgiven i n Fig 8.2, it i s obsened that

this c o r n p o u ~ ~is d found t o be thermally stable up to 2300C

indicated by a well defined plateau. The initial decomposition is

seen starting at 230oC ( T i ) and

peak temp (T,) of 288".
to 42.30%. In this stage a mole

progressing

till 310C

(Tf) with a

The weight loss during this stage amounts

of en escapes from the adduct. The

s seen commencing immediately a t second stage of decomposition i

3 10oC and ending a t 3800C. This stage could be attributed to the
decomposition of [Ni(ox)], to yield t h e final product as NiO. The weight loss during this stage amounts to 21.50% which does not
agree with the calculated value of 34.83% for the loss of some gaseous products This is because the second stage is actually getting initiated before the completion of the first stage. The
residual mass of 36.20% (expected for NiO) observed is i n good

agreement with the theoretical value of 36.14%. The decomposition

features arc summarized below and are tabulated in Table 8.2.

4n

119

200

?go

3bb

UP

52b

$80

760

T m p r r k . . LC

Fig 8.2. The t hernogram (TG/DTG) of [Ni(en)(o~)],~ in N2

decomposition is starts at 2000C (Ti) and progresses till 310oC (Td.

Thc loss 111 nlass curresponding t o h s decomposition stage amounts
to 26.20ah.

This stage of decomposition is due to t l ~ e breaking of the

Ni(I1)-pq.ridylN bond and a mole of pyridine moiety escapes from the complex. The second stage is seen operating a t 3 100C I T , ) and e n d
at 370cC (Tr) with a mass loss of about 49.35% which i si n perfect

match with the cdculated value of 49.56%. This stage could be

attributed to the decomposition of [Ni(pylz(ox)], to NiO and some gaseous products. Above 3700C, a residue was formed whlch is seen
stabIe in the nitrugen atmosphere. The decomposition features are

summarised below and tabulated i n Table 8.5.

Fig. 8.5 The Thernograrn (TG/ DTG] of [Ni@g)~vxh, ~ T N:! L

[ N ~ ( P Y ~ ( O ~ ) ~ I I 4 NiO + py -. gaseous products 310 - 370%

,N,

?... (8.1 1)

366

---.-.-

Clinpttt8

Table 8.7. Thermal characteristics of [Co(H2O)z(oxfi

Temp

Peak
temp PC1
Stages

Wt. loss

(%'

Compound
-

range

PC1
185-225

Found
I
II 19.45

Calcd
19.63

Probable reaction
eq 8.14

215
316

ICOIH~OIJ(OXIJ~

00-34
Above 345

39.25
41.30 (residue)

39.36

eq 8.15

40.96 (residue)

coo

8.2.1.4.

Lewis-base adducts of cobalt(XI]oxalate

The thennogram is given i n Fig. 8.8. It shows an initid decomposition starts

at 5OoC [Ti) and

progresses till i l O o C ( T r ) with

a peak temperature of 98oC ITa).The weight loss corresponding to

this decomposition stage i s 8.10%, which i s in good agreement with

the calculated value of 8% for the loss of one mole of lattice water

from the adduct. The second stage of decomposition is seen initiates

at 230QC (T,) and ends a t 3000C

(Ti).The peak temperature ( T , )of

this stage is 2900C. The mass loss corresponding to this

decomposition stage i s 26.79%. This mass change could be
attributed to t h e liberation of an axial ligand (en) by brealdng the M-

N bond on constant heating. The mass loss calculated for the

expulsion of a mole of en from the adduct was 26.68% which is in
prefect match with the observed value of 26.79%. The third stage of

decomposition is starts at 3000C ( T i ) a n d ends a t 4700C

( T d with a

m a s s loss of 3 1.71% which is in close agreement w i t h the calculated

value of 32.02?10. This mass char~gecould be attnbuted to the

decomposition u i ICo(ox)j, to yield COO as the final product. The

the adduct,

A well defined horizontal region after the first stage

decomposition in the range 100-190W supports the stability of [Co(phen)(ox)],.The authenticity of the product after the first stage

decomposition i s also confirmed by spectroscopic analysis of the

product at this stage.

Fig. 8.10. The thennogram (TG/DTG) ~ f / ( C ~ l p h n ) ( a ) ) .in ~n N 2

The second stage is seen commencing only at 1900C and ending a t 2700C with a peak temperature of 268oC IT,). This stage of
decomposition is due to the breakmg of metal-phenanthrohe N bond

and the mass loss observed during this stage is 25.40% which is not in agreement with the theoretical value of 54.58% for the loss of one mole of phen moiety from the adduct. This is because of the initiation
of thc third stage before the completion of the second stage. The third
stage of decomposition i s seen startmg a t 270oC and ending at 6300C.

This stage could be attributed to the decomposition of [Ca(ox)],to COO

and gaseous products. The residual mass of 20.80% observed in the
thermogram is in good agreement with the theoretical value of 20.63%

respectively. The weight loss correspondirlg to the first stage

decomposition was 33.48% which could be attributed to the loss of a

pn moiety from the adduct leaving back [Co(ox)J,(expected : 33.53%).

Fig. 8.1 3 . The thennogram (TG/DTGJ of [ C O ( ~ ~ ) ( O X ) ] ~

The second stage of decomposition was attributed to the

decomposition of /CO[OX)]~ to COO and some gaseous products. The

weight loss observed in this stage was 32.96%, which is in perfect

match with the theoretical value of 32.57%. The residual mass after
the complete decomposition was found to be 33.56% is in good

agreement with the calculated value of 33.90% expected for COOThese values are tabulated in Table 8.11 and probabIe reactions
are surnmarised below.

ox)],

A ,Nz
290 - 4 4 0 ' ~

COO + gaseous products

.... ... (8.24)

Tclble 8.1 I . Thermal characteristics of[Colpn)(oxJl,

~niedDissociztion Feu tnres o f

0;rrlbt t C o m p b o f Nt.1)Co(I1) and CdII) a d . . ...... 373

W t . loss(%)

Found
245-290

Calcd
33.53
32.57

Probable reaction
eq 8.23
eq 8.24

280

33.48 32.96 33.56 (residue)

I1
A bovc

33.90 (residue)

8.2.1.5

Thermal decomposition of copper(1I) oxalate i n N1

From the thermogram g v e n in Fig.8.12,it is observed that this compound is thermally stable upto 2900C indicated by a well
defined plateau.
starting a t 2900C

I t has only one stage of decomposition which i s

(T,) and ending at 3350C ( T r ) with a peak temp of

332%

IT,). The weight loss during this stage amounts to 48.47%

which is perfectly match with the theoretical value of 47.52%. This

stage could be attributed to the decomposition of [Cu(ox]], t o

CuO and

some gaseous products. The residual mass was found to be 51.53%,

expected for CuO and was in good agreement with the calculated
value of 52.48U/~. The decomposition features are surnrnarised below
and are tabulated in Tabk 8.12.

374

Chapter 8

Fig. 8 . 12 The Thermograrn (TGiDTG] of

in N2

A.N,
[Cu(ox]].
290 - 335 Oc1 CuO
+

gaseous products?

....... (8.25)

Table 8.12, Therrnal characteristic o f [Cu(ux)jn

-

Compound

Temp range

Peak

(%I
Found
I
48.47

Probable
reaction

Calcd
47.52

eq 8.25
CUO

Above

51.53 (residue)

52.48
(residue)

8 . 2 . 1 . 6
(a)

Lewis-base adduc ts of copper(I1) oxalate

((Cu(en)(o?cl).2H~0],,53

The thcrmogran of the adduct 1s given i n Fig. 8.13. It shows

a three-stage decomposition pattern starting from 750C and ending
at 2450'2.

The first stage was observed in the range 75-1050C, while

the second ,md third stages were i n the ranges 185-200OC and

fiermaf Bissociation f O&te Cornpt+ ofM(IIJ CO(II) and ~ 4 ( I f a 375 - Feature o - ) d ... .....-

200-245T respectively. The weight loss correspond to the first

stage d~composition was 14.20 "/u which could be attributed to the

loss of two moles of lattice water from the adduct (expected :

14.54%). In the second stage of decomposition a mole of en escape

from the adduct leaving [CU(OX)]~ back

The third stage of

decomposition could be attributed to the decomposition of (Cu(ox)j,

to CuO and some gaseous products. The loss i n mass during the

second stage was found to be 18.15% whereas that i n third stage

w a s seen to be 35.47"/0. This indicates that before t h e completion of

the second stage, the third stage is getting ~ ~ i t i a t eThe d . calculated m a s s losses for the second and third stages are found to be 24.24%
and 29.09"/0 respectively. The mass of the residue after the

complete riecoinposition w a s 32.18/~, which is in perfect agreement

wit.h calrulated v d u e of 32.13% cxpcctcd for CuO. These values are

tabulated in Table 8.13 and probable reactions are surnmarised

below:

Fig. 8 . 13. The t/zermogram (TGIDTGJ of[(Cu(en)(ox)). ~XZO]~I in N2

[(Cu(en)(ox)).2HzO]n

A ,N, 75 - 105OC

[Cu[en)(ox)]. + 2H20

..-. (8-261

[CU(Q~)],

A ,N,
ZOO - 245 OC

CuO

gaseous products?

... . (8.28)

Table 8.13. Thernzal characteristics of /(Cu(en){ox)).ZH20l,

1 ;

Compound

$
75-105 ("c)
185-200

::Fa&-S
Wt. loss (%I

Probable

iGcl 98
198

I
1I

Found 14.20
18.15

Calcd 14.54
24.24
29.09

reaction eq 8.26
eq 8.27
eq8.28

i(Cu(en)(ox)).2H.>Ol,

2I10-245
Above
245

235

I11

35.47
32.18
(residue)

32.13 (residue)

cuo

(Cu(bipy)(oxll,, 54 From the thennogram given in Fig. 9.14, it i s observed that

this cornpound is thermally stable upto 230QCindicated by a well

defined plateau. This adduct has only one decomposition stage and
is seen starting a t 230OC

(T,) and ending at 260oC (TI). 'The

weight

loss during this stage amounts to 74.34% and this is in good

agreement

w i t h the calculated value of 74.15%. This stage could be

attrlbutcd to the escape of a mole of bipy moiety from the adduct

tugethcr with some gaseous products leaving a residual mass of

25.66% expected for CuO. The observed value (25.66OA) is perfectly

match w i t h the theoretical value o f 25.85%. The decomposihon

features are sumrnarised below and are tabulated in Table 8.14.

Fig.8 . 14. The t hernogrant {TG/DTG] o f /Cu(bipy)[ox& in N 2

ICu(bjpy)(ox)Jn

' CuO + bipy + gaseous productsT..(8.29)

230 - 260 O C

r--Cr~n~pound

Table 8. 14 Thermal churactefistics of [ C ~ { b i p y l ( ~ x ) ] ~

range

reaction

The Thermograrn of the adduct is shown i n Fig.8.15. The

initial decomposition is seen starting a t 200oC (T,) and progressing t i U
300oC [Td with a peak temperature

( T , )of 2700C. The weight loss

(ii)

F'ig 8.18. Iog(g(ol)/ P I us I OOO/ T plots for the thermal decomposition of

Lewis-base adducts of cobalt(~) oxalate 4 1

(1)

Stage I (ii) Stage 0

(iii) Stage LII (a)[(Co(en)(ox)). Hz0In48

(b) [Co(bipy)(ox]]n 4 9

(c)((Co(ph e n ) ( ~ - ~ ) ) f l 250 0 ] ~ (d) [Colpn)(~x)]~ 52

Fro 8. I Cl.

log{g(aJ/T2)U S 7 000/ T plots for !lie thermal dsmrrtposition of

Lewis-base adducts of copper(1Ij oxalate 42 (t) LSage I (ii]

Stage
1 1

(iii)

Stnge

1 1 1

(a] [(Cu(en)(ox)).2H20],,

53

(b)/Cu ( b y y ) { o x h 54 (c) ( C ~ @ h e n ) ( o x )55 ] ~ (d)[Culpnllo~)]~~ 57

The activation energies (Ea) for the different stages of

thermal decomposition of the Lewis-base adducts of nickel(I1)

oxalate

are

i n the

range

86.10 to

376.33 kJ/mol.

The

corresponding values of eiltropy of activahon (AS) fall in the range

-2.93 to -238.09 J/K/mol The pre-exponential factors vary in the

Table 8.1 7

Kinetic parameters for the thermal decomposition stages o f Lewis-base adduct of nickel(0) oxalate

Compound

Stage I

Stage

I1

Stage 111
i

Ea kJ/moI

A
5-1

AS J/K/mol

Ea kJ/mol

A
s-1

AS

J/K/mol

Ea kJ/mol
-

A
s-I

AS J/K/mol

[Ni(en](ox)].

188.36

48558.28

-160.46

213.87

15443.95

-171.36

[Ni(bipyj(ox]]n

229 68

28247.52

-166.74

[(Ni(phen)(o~)].2H2@]~ 95.94

2855.14

-179.65

377.26

-2.93

376.33

IN~[PY)~(OX)~~
[(Ni(pn)(ox)). HzO]n

97.17

4.35

-238.09

313.33

3.57

-87.45

86.10

53.54

-2 13.60

128.98

28.92

-223.46

Table 8.18. Kirtetic parameters for the thennu! decomposition stages of Lewis-base udducts of cobalt(11)

r---Compound

oxalate

Stage 1

Stage 11

Stage 111
AS

t-

Ea
kJ/mol

J/K/mol 1.14

Ea kJ/mol

A s-1

AS J/K/rnol

-I

6'90 10-2
-274.74
-

[(Co(en)(ox)).H201n

57.75

-246.20

88.75

2.32

-243.26

77.45

177.54

1 1899.36
237.16

- 173.39
.

88.28 [{Cofphenj(o~)).HzO]~

-201.17

227.78

3047920

- 125.6 1
-

Table 8.20 CurreIation Coefficient calculated using the nine firms of g(a)for fhe Lewis-base adducts of nickel(U) and cobalf(11)omlate Stage I
1 !

Form of g[a}

[(Pii(phen) [Nl(py)~ INi(4(ox)ln I N ~ ~ ~ P Y ) ( Q X )I~ (oX)).2H20~n (0x)ln -0.989153

-0.9963682 -0.990279 ' -0.993527

[(Nibn) (ox)).H2OJn
-0.986852

(OX)].

[(Coknl HD],

ICOUJ~PYI

(ox)].
0.983746

j(Co(phen) (~x]].HaO]n
-0.990866

ICo@n1 OX)]^
-0.994568

uZ

-0.994012

a+( 1 -a)

Wl

-0.989531

-0.996410

-0.990787

-0.993872

-0.987285

a 1

-0.994268

-0.984612

-0.991209

-0.994839

1 - 12

-0.986757

-0.995432

-0.987383

-0989539

-0.981513

1354 -0.989845 -0.98

-0.987753

-0.993457

(1- j-a)-

-0.989658

-0.996450

-0.99085 1

-0.994058

-0.987435

-0.994375 -0.9848 17

-0.991333

-0.994850

(1-~1)2/3

-h(l-CI)
1

-0.989 139
-0.9867 3

-0.996 108

-0.9904 13

-0.993285
-0.989058 -0.979455

-0.986034

-0.9934 19
-0.988390

-0.985281

-0.99052 1

-0.994803

a ]1
11

-0.995067

-0.987805
-0.9833 19

-0.98009 1

-0.983 185 -0.98 1530 -0.983963

-0.484649

-0.986893
-0.98 14 16

-0.993668
-0.992439 -0.994466
-0.994564

-0.982809
1

-0.994034

-0.970962 -0.985270
-0.985477

-0.976298

1-(l..a) 112
1- ( l - ~ ) l J 3

-0.9886 14

-0.996085
-0.996155

-0.989826
-0.989969

'

-0.992604
-0.992867

-0.99282 1
-0.993066

-0.990003

-0.988668

-0.990208

Table 8.21. Correlatior~coeJficient caIcutaled by the nine f ~ m oJ g(a) for the Lewis-base adducts of nickel(1I)~ l n d cobalt(11) oxalate Sage D
Form of g(u)
iEi(enllax)l. -0.997508

P
-0.993769 -0.993059

uZ
a+(l-a) ln(l-a)
/ l -(l-a)1/3]*
2 (1- 7 a)-(1- U ] Z / ~

-0.997580

-0.993031

-0.998059

-0.989258

-0.987085

-0.990536

-0.999 196

I
-0.996834 -0,992373
.

-0.992232 -0.997935
-

-0.985800 -0.989468
4

-0.977395 -0.987283

-0.990717

-0.998387

-0.997624

-0.994 113
-0.993887
-0.992527 -0.990250

-0.993 109
-0.992509

-0.9981 30
-0.997790

-0.985646
-0.9897 14

-0.999241
-0.998963
-0.997999

-In ( 1-a)

-0.997560
-0.996999

-0.987017
-0.982143

-0.985335
-0.975036

[-In(1 -a]]l/2
[-ln(1 -a]]1'3

-0.991809 1-0.997726

-0.984739 -0,976152
-0.98894 1
-0.989224

-0.996047
-

-0.99 1 128

-0.996760

-0.972649

-0.95381 3
-0.98408 1

-0.992502
-0.998916
-0.999059

I-(I-u]'/~
1-(I -a]'13

-0.997354

-0.993600
-0.993562

-0.99254 1
-0.992642

-0.997957 -0.987452
-0.997829
-0.987267

-0.997353

-0.984402

Table 8.23. Correlation coefficient calculated using the nine form of g(a) for the Leruis-base adducts of copper(D1 oxalate
Stage I

Stage I1

Stage

I11

Form of g(a)
U*

[iCuien)(ox)' [Cu[bipy)(ox]]n ICu(phen)(on)jn [(Cu(en)(ox)l.2 [CU(~II)(OX)]~ ICutphenl(ox)ln !(Cu(en)(ox)j.2 2HzOjn H70]n H2O]n
-0.987752

-0.994389

-0.996262

-0.992888
-0.993 167
-0.99 1494

-0.987715

-0.999 139

-0.991701

a+(l-crj ln(1-a)
[l-(l-a)l/3]2

-0.988013

-0.99428 1

-0.996429
-0.993324
-0.996486

-0.988026
-0.985679
-0.988030

-0.999 172
-0.998344

-0.99 1899
-0.990394

-0.985 127 -0.988 134

-0.987716

-0.99381 1
-0.994429

(1 - $ a]-(1-a]2/2
-ln(l-a)
[-In(1 -u)ll~~

-0.993305 -0.993 1 13 -0.99 1567

-0.9992 13 -0.998856 -0.997388 -0.99 1769

-0.99 1973
-0.991648 -0.99023 1

-0.993677

-0.99568 1
-0.992200

-0.987637
-0.985616

-0.984706
-0.98 1050 -0.98700 1

-0.993058 -0.99 1766

-0.994149

I-In(I-a)]lf3

-0.97604 1
-0.995243

-0.989738
-0.99273 1

-0.982333
-0.987200

-0.988898
-0.99 142 1

1 - ( I -a)l/z

-0.998859 -0.998767

1 -[I-a]]!]

-0.987133

-0.993529

-0.995472

-0.992817

-0.987416

-0.99 1590

392

Chapter 8

From t h e corr~cfaliuncoefficients obtained from the kinetic

studies ( a v e n in Tables 8.20-3-23), it was evident that the rate

co~~trolling process during the thermal decomposition of t h e

complex is represented by g ( a )

(1-2/3a)-(1-a)3/2 in most cases

corresponding to three-dimensional Musion, spherical symmetry;

obeying 'Ginstling-Brownshtein' equation. But only i n the case of

decomposition of [Co[bipy)(ox)l,,the rate controlling process has
been obeying Mampcl equatio11(26)or Random nucleation, one

nucleus on each particle. The form of g ( a ) with the highest value of

correlation coefficients and the corresponding rate controlling
process are tabulated and are presented in Tables 8.24-8.27.

References 1.
2.

D. Dollimore, Thermochim. Actu; 117 (1987) 33 1

J. E. House and L. A. Marquardt, J. Solid State Chem; 89

(1990) 155

3.

N. Deb, N. N. Dass and P. K. Gogoi, Thennochim. Acta; 198 (1992) 395

4.

D. Dollimore and T. A. Evans, Thermochim. Acta; 178 (1991) 2 6 3

D. Dollirnore and T. A. Evans, Thermochim. Acta; 179 (1991) 49

5.

6.
7.

D. B. Bent, D. Dollimore, J. Dollimore and T. A. Evans, J. Chem. Soc. Faraday. Trans; 87 (1991) 16 1 P. A. Prasad, S. Neeraj, S. Natarajan and C. N. R Rao, Chem. Commun; 14(2000) 1251
C. G. R. Nair and (1978) 161

8.

K. N. Ninan, Thermochlm. Acta; 23

9.
10. 11.

E ; . Nagase, Bull C k r n . Soc. Japan; 45 (1972) 2166

M. A. Gabal, Thermochim. Acta; 402 (2003) 199 E. 3. M. Diefallah, M. A. Gabal, A. A. E. Bellihi and N. A. Eissa, Thermochim. Acta; 376 (200 1) 43

12.

R. Shen, H. Shen, Y. X. Pan, T. F. Chen and X. E. Cai, Inter J. Research in Phys. Chem and Chern. Physics; 215
B.

(2001) 1413
13.

B. Mdecka, E. D. Ciesla and A. Malech, J. Them. Anal and

Calori; 68 (2002) 819

E. I . Stocka and A. Grabowska, J . Therrn. Anal and Calori; 54 (1998) 115

P. Roman, A. Luque and M . L. Seco, Thermochim. Acla; 257 (1995) 67

J. Li, F. X. Zhang, Y. W. Ren, Y. Q. Hun and Y. F. N a n , Thermochirn.Actu; 406 (2003) 77

N. Rajic, D. Stojakovic and R. Gabrovsek, J. T h e m . Anal

and Calori; 63 (2000) 19 1

D. C. Sulikowska, J. R. Doczekdska and J. Them.. Anal and Calori; 60 (2000) 145

11995) 205 2. Sieber, S. Dccurtins, C . Wilson a n d 6 (2000)36 1

M. Markiewicz,
258

V. Jordanovska and R. Trojko, Thermochim. Acta;

D.Yufit, Euro. J. Chem;

W . W. Wendlandt, "Thermal Analysis", Wiley-Inter Science, New York, 3 r d Ed; (1986)

K. N. Ninan and C. G . R . Nair, Thermochim. Acta; 37

(1980) 16 1

A. A. Froast and R. G. Pearson, 'Kinetics and Mechanism" Wiley, New York, (1961)

T. Gangadevi, K. Muraleedharan and M. P. Kannan, Thermochim. Acta; 146 (1989) 225 K. K , hravindakshan and Acta; 155 (1989)247

K. Muraleedharan, Thermochim

S. Mathew, C. G . R. Nair and K. N. Ninan, Themochirn Ada; 32

( 1965) 386

Chapter 9 Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates

9.1

but also have extended conjugative interaction spanning from one carboxylate to the other, through the two ends of the aromatic ring. While the carboxylate moieties in all the three isomers can have the same versatile bonding features like in any other carboxylate systems, the conjugatively coupled aromatic ring can function as an interesting spacer moiety between the COOH functions in them. Among the three isomers, the 1,4-isomer terephthalic acid (H2tpa), HOOC-C6H4COOH, has got the two COOH moieties disposed in opposite directions. It is easy to understand that the dianion of 1,2- and 1,3- isomers will result in the formation of zig-zag type polymer metal dicarboxylates. On the other hand, the 1,4-isomer has the possibility of generating linearly coupled coordination polymers. Besides the usual variations possible in the linking modes of the carboxylate moieties, the phenylene function will act as a rigid and electronically interacting spacer unit through its -system, leading in polymeric metal terephthalates which can be expected to have a metalmetal separation of about 12 . Almost all metal-tpa complexes are binuclear or polymeric in nature except in a few cases where they exist as discrete complexes.(1) Several metal terephthalates with 1D-(2,3) and 3D-(4-6) framework structures have been
7)

Introduction
hthalic acid and its two other position isomers are yet another class of compounds which are akin to oxalate systems in terms of their extended conjugation. Not only these dicarboxylate systems have rigid framework

reported. Structural prediction of several interesting metal terephthalates of Mg, Mn, Fe and Co have been carried out by Monte Carlo Simulated techniques.( In a layered complex, [Co2(OH)2tpa],(
3)

two types of edge sharing CoO6 chains

connected to each other by -OH moiety (Co-O-Co bridges) exists which form layers that are further joined together through terephthalate anion and exhibits interesting magnetic properties from paramagnetism to metamagnetism and even having collinear antiferromagnetism. However, [Co(H2O)2tpa](3) which contains layers of octahedral CoO6 connected via Co-O-C-O-Co shows only paramagnetism. Many copper and cobalt terephthalate complexes find wide applications as gas adsorbents and as metamagnets.(8) Recently Dale and coworkers(9) reported a threedimensional complex, [Pb(tpa)(H2O)]n, hemidirected seven-coordinate, wherein both Pb geometry is seen to be having monodentate and bidentate

402

Chapter 9

carboxylate coordination modes. Several interesting terephthalate bridged mixedligand complexes with 1D zig-zag chain(10-17) and 3D supramolecular structures with channels are known. Recently Xiao et al(21,22) have reported interesting 1Dlinear tpa bridged complexes of the type [M(tpa)Cl2(phen)2(H2O)n] [M= CoII or CuII; n = 0, 2]. Several extended binuclear Fe(II) complexes, [Fe2(tpa)(L)4](X)n [L = 2,2'-bipy, phen, pn, n-phen, me-phen; X = SO4, ClO4; n = 1, 4], are known in which tpa dipn(N-(3-aminopropyl)-1,3-diaminopropane)], tpa functions as bisacts as bidentate linking ligand.(23) In the dinuclear [Cu2(tpa)(L)4](ClO4)2(24a,b) [L = monodentate moiety while in [M2(tpa)(L)4](ClO4)2(24c,d) [M = Cu, Ni, Co; L = bipy, phen], tpa is seen to be existing in bidentate linking mode. Recently Rogan et al(25) reported an interesting one-dimensional polymeric Cu(II) complex, bis[Cu(tpa)(phen)(H2O)]n in which tpa is found to be acting as

monodentate species. Also reports are available on several interesting dinuclear Mn(II) systems with composition [Mn2(tpa)(L)4](ClO4)2(24c,26) [L = phen, bipy] having 1D chain and showing antiferromagnetic behaviour. In the dinuclear Ni(II) complexes [Ni2(L)(L')4](ClO4)2.nH2O(27) [L = xtpa or btpa (bromo or iodo terephthalate dianion); L' = 2,2'-bipy, phen, n-phen; n = 0, 2] tpa functions as bidentate bridging moiety whereas in imidazole), tpa acts as = Cu, Mn; [Ni2(tpa)(pn)4(Him)2](ClO4)2(24a) (Him = bis-monodentate function. In [M(L)4(H2O)2]tpa(28,29) [M L = imidazole], tpa is found to be non coordinated and links

the cations through H-bonding network. Recently Pang et al(30) reported an interesting two-dimensional system [Ni(bipy)(H2O)4]tpa with sheet-like structure in which tpa dianions are found to be non-coordinated. There also exist several 3D complexes wherein this non-coordinated nature of tpa is seen.(31,32) Quite many of the mixed-ligand tpa bridged complexes of Cu, Co, Ni, Fe and Mn are seen to be showing predominantly antiferromagnetic property.(12,23,24,27) A 3D supramolecular framework system, [Mn(tpa)(bipy)(H2O)]n, recently reported by Zhang et al(33) are shown to have tpa as tridentate moiety. Yaghi et al(34) have also reported an interesting cluster compound, [Zn4O(tpa)3].8DMF.C6H5Cl, which contains [OZn4] clusters. This chapter focuses on some of metal terephthalates which are polymeric in nature and their interaction with various Lewis-bases with an idea of generating interesting mixed ligand complexes.

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates

403

9.2.

Experimental

9.2.1 Reagents
Terephthalic acid, CuCl2.5H2O, NiCl2.6H2O, pyridine, were of Merck quality. 2,2'-bipyridine,

1,10-phenanthroline monohydrate, ethylenediamine and 1,3-diaminopropane used Methanol, acetone, and diethyl ether were used after purification by known procedure.(35)

9.2.2 Preparation of Terephthalate Complexes of Cu(II) and Ni(II)

(a) Copper(II) terephthalate complex, [(Cu(tpa)).H2O]n, 58 To an aqueous solution of disodium terephthalate then digested on a water bath. (0.21g, 1mM),

cupric chloride (0.17g, 1mM) in 10 ml methanol was added slowly with stirring and The solution pH was adjusted to 6-7 by using (yield NaOH solution. Light blue coloured complex was formed which was washed repeatedly with water followed by methanol. It was dried under vacuum over P2O5. : 85%) (b) Nickel(II) terephthalate complex, [Ni(tpa)(H2O)2]n, 59 The preparative procedure adopted for this complex was also similar to that employed for the copper(II) complex. A solution of nickel chloride (0.23g, 1mM) Light green complex was was added slowly with stirring to 1mM aqueous solution of disodium terephthalate. Its pH was adjusted to 6-7 by using NaOH solution. was then dried under vacuum over P2O5. (yield : 80%) Attempt to prepare cobalt(II) terephthalate complex by above procedure was not successful. precipitated out. It was washed repeatedly with water followed by methanol which

9.2.3. Preparation of Lewis-base adducts of copper(II) and nickel(II) terephthalates

404

Chapter 9

(a)

[Cu(en)2]tpa.2H2O, 60 A solution of en (0.13ml, 2mM) in methanol was added dropwise to a

suspension of copper(II) terephthalate (0.24g, 1mM) in methanol with constant stirring for about 1 h. A clear dark violet solution was obtained which was filtered and concentrated to half of its volume and then cooled. dried under vacuum over P2O5. (yield : 80%) (b) [Cu(bipy)2(H2O)2]tpa .4H2O, 61 About 0.31g (2mM) of 2,2'-bipy in methanol was dissolved in 10ml methanol and was added to a suspension of copper(II) terephthalate (0.24g, 1mM) in methanol. The mixture was kept under reflux for about 1 h. A clear blue solution was obtained which was filtered and concentrated to half of its volume and cooled. The complex separated out as blue solid which was filtered and repeatedly washed with ether. It was dried in vacuo. (yield : 85%) (c) [Cu(phen)2(H2O)2]tpa. H2O, 62 The method adopted for the preparation of this complex was almost similar to that one employed for the 2, 2'-bipyridine adduct. Instead of 2,2'-bipyridine, 0.4g of phen in methanol was added to a copper(II) terephthalate suspension in methanol. The complex was separated out as green powder and was repeatedly washed with ether. It was dried under vacuo. (yield : 80%) The complex was separated as violet solid and was filtered. It was repeatedly washed with ether and

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates

405

(d)

[Cu(py)2tpa]n, 63 A solution of pyridine (0.48ml, 3mM) was added to a copper(II) terephthalate

(0.24g, 1mM) suspension in methanol with constant stirring. The reaction mixture was refluxed for about 3h. out by filtration. The colour change of the parent complex gives clear indication of the formation of new adduct. The sky blue complex formed was separated It was washed repeatedly with methanol followed by ether. The complex was dried in vacuo. (yield : 75%) (e) [Cu(pn)tpa]n, 64 A solution of pn (0.27ml, 3mM) in methanol was added dropwise to a suspension of copper(II) terephthalate (0.24g, 1mM) in methanol with constant stirring for about 3 h. A clear blue solution was obtained from which bulk quantity of blue solid was found to be thrown out from the solution. It was washed with methanol followed by ether and dried in vacuo. (yield : 80%) (f) [Ni(en)2(H2O)2]tpa, 65 A solution of en (0.13ml, 2mM) in methanol was added dropwise to a suspension of nickel(II) terephthalate (0.25g, 1mM) in methanol with constant stirring for about 3 h. A clear pinkish violet solution was obtained which was filtered and concentrated to half of its volume and cooled. The complex was separated as pinkish violet solid and was filtered. It was repeatedly washed with ether and dried under vacuum over P2O5. (yield : 85%) Attempts to prepare the other adducts of nickel(II) terephthalate with bipy, phen, py and pn were met with failure by this method. cobalt(II) terephthalate adducts could also be separated. Similarly none of the

9.3.

Results and Discussion

9.3.1 Metal terephthalates of Cu(II) and Ni(II)

Even though the aliphatic dicarboxylic acid such as succinic, malonic and oxalic acid form complexes with metals like Ni(II), Co(II) and Cu(II), the aromatic dicarboxylic acid such as terephthalic acid was seen to be resistant in the complex

406

Chapter 9

formation with metal like Co(II) by conventional route. However it forms complexes with Cu(II) and Ni(II). The composition of Cu(II) and Ni(II) complexes of terephthalic acid obtained was determined by elemental analysis and the water content determined by TG analysis. The data are tabulated in Table 9.1 Table 9.1 Elemental analytical data of metal(II) terephthalates
Elemental content (%) obsd (calcd) C [(Cu(tpa)).H2O]n (CuC8H6O5) 58 [(Ni(tpa)(H2O)2).H2O]n (NiC8H10O7) 59 245.54 276.69 39.10 (39.01) 34.71 (34.69) H 2.50 (2.44) 3.65 (3.61) M 25.9 (25.8) 21.3 (21.2) Light blue Light green

Complex (Emp. formula)

Formula weight

Colour

The broad band at 3175 cm-1, (O-H) in the free ligand, [H2tpa] was found to be absent in both the metal(II) terephthalate complexes. This was indicative of the deprotonated form of the tpa group in the meal complexes. Broad peaks in the range 3400-3380 cm-1 were seen in both complexes which gave a clear indication of the presence of lattice water in the system. The peak seen at 3230 cm-1 was assigned to coordinated water in nickel(II) tpa complex which was not seen in the copper(II) tpa complex. The characteristic as(CO2) bands were seen to appear in these complexes in the region 1570-1560 cm-1 while their s(CO2) peaks were found in the range 1392-1385 cm-1. As mentioned earlier the band separation around 180 cm-1 indicates bidentate coordination modes of both carboxylate groups of tpa(36) (Table9.2). Table 9.2. IR spectral data of metal(II) terephthalates (cm-1)
Complex H2tpa [(Cu(tpa)).H2O]n (O-H) 3175 3380 (O-H) 1610 1620 as(CO2) 1698 1570 S(CO2) 1463 1392 235 180

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates [(Ni(tpa)(H2O)2).H2O]n 3400 1630 1560 1385 175

407

The electronic spectra of metal(II) terephthalates could be recorded only in the solid state because of their insoluble nature. The absorption values are given in Table 9.3. The nickel(II) tpa complex gave characteristic peaks which are typical of octahedral nickel(II) complex.(37,38) The copper(II) tpa complex showed a broad absorption band at 13680 cm-1 which is expected for a square planar complex.(39,40)

408

Chapter 9

Table 9.3 Electronic spectral and magnetic data of metal(II) terephthalates

Complex [(Cu(tpa)).H2O]n Absor. max

(cm-1)

Assignments
3B 3A 1g

eff
(BM)

13680 10820

2A1g
3T (F) 2g 3T (F) 1g

1.49 1 2 3 2.85

2g(F)

[(Ni(tpa)(H2O)2).H2O]n

14830 25640

3A 3A

2g(F)

2g(F)

3 T1g(P)

Magnetic measurements showed that both Ni(II) and Cu(II) terephthalate complexes are paramagnetic in nature ( Table 9.3 ). The [(Ni(tpa)(H2O)2).H2O]n eff value of was found to be 2.85 BM indicating that the complex is

octahedral in nature while the eff value for [(Cu(tpa))n.H2O]n was found to be 1.49 BM which is slightly lower than the value expected for typical Cu(II) complex . All the foregoing data indicated the four coordinated character for copper(II) and six coordinated character for nickel(II) complex. Based on the above observations and high insolubility, the overall structure of the metal terephthalate complexes could be considered as polymeric in nature.

9.3.2 Lewis-base mediated fragmentation of copper(II) terephthalates

The set of Lewis-bases chosen for the interaction studies with polymeric copper(II) terephthalates, were the same as those used for other systems. We have carried out the interaction of Lewis-bases with Cu(II) and Ni(II) terephthalates, under various reaction conditions and stoichiometric proportions as earlier. However, to isolate the new structural species we have employed some optimum reaction conditions. These along with some salient features of the reactions and products isolated are presented in Table 9.4. As indicated in Table 9.4 and in the preparative section, the adduct formation and breaking up of the polymeric network occur with comparative ease with en, bipy, phen and pn at the addition of the ligand itself. However, py does not seem to depolymerise the metal terephthalates. The analytical data shown in Table 9.5 confirm the 1:2 (copper(II) terephthalates : Lewis-base) composition for all the adducts except for the pn adduct which was only 1:1.

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates

409

Table 9.4

Interaction of metal(II) terephthalates with various Lewis-bases (LB)

Conditions stirring, RT, (2h) stirring, RT, (1h) stirring under reflux, (2h) stirring under reflux, (1h) stirring under reflux, (2h) stirring under reflux, (1h) stirring under reflux, (3h) stirring under reflux, (3h) stirring under reflux, (3h) stirring, RT, (2h) stirring, RT, (3h) stirring, RT, (2h) stirring, RT, (3h) Observation partial dissolution to give light violet solution complete dissolution (clear violet solution) partial dissolution (light violet solution) complete dissolution (clear light violet solution) partial dissolution (light violet solution) complete dissolution (clear light violet solution) no observable change slight colour change from blue to light blue (incomplete reaction) colour change from blue to sky blue (solution colourless) partial dissolution (light blue solution) complete dissolution followed by blue solid separation partial dissolution (light violet solution) complete dissolution (clear violet solution) [Cu(py)2tpa]n. (63) Products Separated no stoichiometric compound [Cu(en)2]tpa.2H2O (60)

Metal terephthalates +LB (in MeOH) 58 + en (1:1) 58 + en (1:2) 58 + bipy (1:1) 58 + bipy (1:2) 58 + phen (1:1) 58 + phen (1:2) 58 + py (1:1) 58 + py (1:2) 58 + (py excess) 58 + pn (1:1) 58 + pn (1:2) 59 + en (1:1) 59 + en (1:2)

no characterisable product [Cu(bipy)2(H2O)2]tpa.4H2O (61) no stoichiometric compound [Cu(phen)2(H2O)2]tpa.H2O (62) no characterisable product

no stoichiometric compound

no characterisable product [Cu(pn)tpa]n (64)

no stoichiometric compound [(Ni(en)2(H2O)2].tpa (65)

Table 9.5

Elemental analytical terephthalates

Complex (Emp. formula) Formula weight

data

of

Lewis-base

adducts

of

copper(II)

Elemental content % obsvd (calcd)

Colour

410 C [Cu(en)2]tpa.2H2O (CuC12H24O6N4) 60 [Cu(bipy)2 (H2O)2]tpa.4H2O (CuC28H32O10N4) 61 [Cu(phen)2(H2O)2] tpa.H2O (CuC32H30O9N4) 62 [Cu(py)2tpa]n (CuC18H14O4N2) 63 [Cu(pn)tpa]n (CuC11H14O4N2) 64 301.6 385.7 678.0 56.60 (56.64) 4.47 (4.46) 8.25 (8.26) 647.9 51.84 (51.86) 4.95 (4.98) 8.60 (8.64) 383.5 37.58 (37.54) H 6.28 (6.30) N 14.62 (14.60)

Chapter 9 M 16.6 (16.5)

Violet

9.7 (9.8)

Dark blue

9.4 (9.3)

Green

55.97 (55.99)

3.66 (3.65)

7.22 (7.25)

16.5 (16.4)

Blue

43.70 (43.75)

4.70 (4.67)

9.30 (9.28)

21.1 (21.0)

Blue

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates

411

9.3.3

IR spectra of Lewis-base adducts of copper(II) terephthalate

The presence of Lewis-bases in all the adducts could be confirmed by the

appearance of their characteristic peaks in the IR spectra. to the values in the parent metal terephthalates.

The peaks due to

terephthalate moiety were also present with some shift in their position as compared The as(CO2) stretching band occurring at 1570 cm-1 in [(Cu(tpa)).H2O]n was found shifted to 15261568 cm-1 in its adducts and the s(CO2) band observed at 1392 cm-1 was found lowered to 1380-1390 cm-1 in its adducts. The asymmetric and symmetric stretching vibrations of NH2 group of en in [Cu(en)2]tpa.2H2O, 60, were observed at 3310 and 3240 cm-1 respectively. The bending mode (NH2) was seen at 1601 cm-1. The sharp band seen at 1040 cm-1 was assigned to C-N stretching. The as(CO2) and s(CO2) bands of carboxylate group were observed at 1547 and 1389 cm-1 respectively and its non-bonded nature is confirmed by their value of 158 cm-1. The weak band seen at 3450 cm-1 indicates the presence of lattice water in it. The IR spectrum of the adduct [Cu(bipy)2(H2O)2]tpa.4H2O, 61, gave new peaks at 775, 1020, 1450 and 1600 cm-1 indicating that bipy are coordinated to Cu through both of its pyridyl nitrogens. The bands at 1545 and 1390 cm-1 are assigned to as(CO2) and s(CO2) vibrations of carboxylate group of terephthalate moiety. The value of 155 cm-1 again confirms the non-coordinated character of the carboxylate group. The in-plane and out-of-plane ring deformation modes of bipy were observed at 650 and 440 cm-1 respectively. The strong band at 3230 cm-1 indicates the presence of coordinated water and the weak band seen at 3400 cm-1 shows the presence of lattice water in it. For the adduct [Cu(phen)2(H2O)2] tpa.H2O, 62, new bands were observed at 724, 1470 and 1613 cm-1 respectively. The bands at 1470 and 1613 cm-1 were assigned to the ring skeletal vibrations of phen and its ring deformation modes were observed at 640 and 435 cm-1 respectively. The asymmetric and symmetric bands of carboxylate group of terephthalate moiety were seen at 1526 and 1380 cm-1. The value of 146

412

Chapter 9

cm-1

show that the carboxylate moieties exist in ionic form. The bands at 3370 and

3220 cm-1 indicates the presence of lattice and coordinated water in the complex. The IR spectrum of the adduct [Cu(py)2tpa]n, 63, shows peaks at 1600 and 1485 cm-1 which were assigned to C=C and C=N ring stretching skeletal bands of pyridine. The as(CO2) and s(CO2) bands were seen at 1568 and 1388 cm-1

respectively. The value of 177 cm-1 confirms the bidentate chelating nature of the carboxylate group. The ring deformation modes of pyridine were observed at 690 and 432 cm-1. For the adduct [Cu(pn)tpa]n, 64, two peaks were observed at 3300 and 3263 cm-1 which are characteristic of asymmetric and symmetric vibrations of NH2 groups of pn. The (NH2) band of pn was observed at 1598 cm-1. The as(CO2) and s(CO2) bands were seen at 1565 and 1391 cm-1 respectively. The value of 175 cm-1 is

characteristic of the bidentate chelating nature of the carboxylate group in the complex. All the other relevant absorption frequencies of copper(II) terephthalate and their adducts are given in Table 9.6. Like in the other systems we have monitored the trend in the changes of both asymmetric and symmetric stretching frequencies of the carboxylate moiety. The order for among the various adducts were found to be 63 > 64 > 60 > 61 > 62. The trend is seen to be almost dependent on the pKa value of the various Lewis-bases chosen(41) and is consistent with the observations made in the adducts of other metal dicarboxylates. Table 9.6 IR spectral data of copper(II) terephthalate and its various Lewis-base adducts (cm-1)
Adducts (O-H) as(CO2) s(CO2) 58 3380 1570 1392 180 60 3450 1547 1389 158 61 3400 3230 1545 1390 155 62 3370 3220 1526 1380 146 63 1568 1388 177 64 1565 1390 175

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates

413 1600 1450 775 1020 440 650 1613 1470 724 435 640 1600 1480 432 690 1036 3300 3263 1598 -

C C C N
(C-N) (C-H) (C-H) (NH2) (NH2) Ring deformation (outplane) (inplane)

1040 3310 3240 1601 -

414

Chapter 9

9.3.4 Electronic spectra and magnetic data of Lewis-base adducts of copper(II) terephthalate
The electronic spectra of various adducts of copper(II) terephthalate were recorded either in solid state or in solution Table 9.6. assignable to the
2B 1g
B

(Fig 9.1). The data are presented in

In the en adduct, 60, a broad band occurs in the region 17790 cm-1 2A1g transition consistent with a square planar

geometry.(39,40) Moreover n bands were found as blue shifted while bands red shifted compared to the parent complex. These bands were found to be appearing in the region 34010 and 39520 cm-1 respectively. In the tetragonally distorted octahedral adducts of bipy, phen, py, pn broad band occurs in the region 14370-17240 cm-1 which is assignable to the 2B1g 2A1g transition consistent with distorted octahedral
B

geometry in these adducts.(42,43) In addition n bands were found as blue shifted and bands red shifted in comparison with the parent complex. These bands appear in the region 33220-34010 and 39210-40000 cm-1 respectively. Further, all the adducts exhibit an intense absorption band in the region 25970-28010 cm-1 which could be assigned to charge transfer transition. The magnetic moment values of the various copper(II) terephthalate complexes vary in the range 1.53-1.80 BM. The eff values for the polymeric adduct were found to be lower than the monomeric species indicating the possibility of some metal-metal interaction in the former.
(44)

In the adducts 63 and 64 which have a polymeric

structure the eff values are seen to be comparatively lower than in others. Evidently they (63 and 64) would be retaining some Cu-Cu interaction present in the parent complex in them.

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates

415

Fig 9.1

The electronic spectra of copper(II) terephthalate and its various Lewis-base adducts (a) [(Cu(tpa)).H2O]n, 58 (c) [Cu(bipy)2(H2O)2]tpa.4.H2O, 61 (e) [Cu(py)2tpa]n, 63 (b) [Cu(en)2]tpa.2H2O, 60 (d) [Cu(phen)2(H2O)2] tpa. H2O, 62 (f) [Cu(pn)tpa]n, 64

416

Chapter 9

Table 9.7 Electronic spectral and magnetic moment data of of copper(II) terephthalate
Adducts Absor.max

Lewis-base adducts
eff (BM)

(cm-1)

Assignments n charge transfer

2B 1g

40650 [(Cu(tpa)).H2O]n 58 32670 25440 13680 39520 [Cu(en)2]tpa.2H2O 60 34010 25970 17790 39060 [Cu(bipy)2(H2O)2]tpa.4H2O 61 33220 26450 14410 40000 [Cu(phen)2(H2O)2]tpa.H2O 62 33333 26040 15170 39680 [Cu(py)2tpa]n 63 33550 28010 14370 39210 [Cu(pn)tpa]n 64 33440 26520 17240

1.49

2A1g

n charge transfer
2B 1g

1.75

2A1g

n charge transfer
2B 1g

1.79

2A1g

n charge transfer
2B 1g

1.80

2A1g

n charge transfer
2B 1g

1.53

2A1g

n charge transfer
2B 1g

1.60

2A1g

9.3.5

EPR spectra of Lewis-base adducts of copper(II) terephthalate

X-band EPR spectra of parent copper(II) terephthalate, 58, and its adducts

were either recorded in solution state (1:1 toluene-methanol mixture) at liquid

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates

417

nitrogen temp or in solid state. The EPR traces are given in Fig 9.2-9.3. The anisotropic features of the spectra in the case of 60, 61 and 62 which are recorded in solution state are evident from the spectra in Fig 9.3. The various spinHamiltonian parameters were calculated from the spectra using DPPH or TCNE free radicals as the g marker. The data are tabulated in Table 9.8.

Field (Gauss)
Fig 9.2 EPR spectra of copper(II) terephthalate and its polymeric adduct in solid state at 77 K (a) [(Cu(tpa)).H2O]n, 58 (b) [Cu(pn)(tpa)]n, 64

The spectra of parent copper(II) terephthalate, 58 and the pn adduct 64, are not resolved enough to get the A value. The spectra of 60, 61 and 62 in solution at 77 K (Fig 9.3) gave well resolved parallel components and unresolved perpendicular components. The hyperfine constant A for these adducts are moderately high at 190 G for 60, 160 G for 61 and 150 G for 62. The comparatively high A for 60 suggests that the electron spin is more localised in Cu(II) dx2-y2 orbital(45) of en adduct 60 than in bipy adduct 61 and phen adduct 62. It implies that in 61 and 62, there is more spin delocalisation onto the Lewis-base. This is very much expected because en is totally -donor while bipy and phen can be considered as donor as well as -acceptors because of their low-lying * orbitals. As phen has

418

Chapter 9

better -acceptor property than bipy, the electron spin gets delocalised more on phen adduct 62 than in bipy adduct 61. The observed trend in -covalency factor, 2Cu value is 60 > 61 > 62. This is also in consistency with the expected order. The low G value of parent copper(II) terephthalate, 58 is an indication of moderate exchange interaction while the G value for the adducts 60, 61 and 62 show absolutely no interaction in them.(46) The nature of the g tensor values g > g > 2.0023 observed for all the Cu(II) adducts indicate dx2-y2 ground state for them.

(a) [Cu(en)2]tpa.2H2O, 60 (b) [Cu(bipy)2(H2O)2]tpa.4.H2O, 61 (c) [Cu(phen)(H2O)2]tpa.H2O, 62

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates 419 Fig 9.3 EPR spectra of monomeric adducts of copper(II) terephthalate in solution (1:1 toluenemethanol mixture) at 77 K

Table 9.8 The various EPR parameters of the Lewis-base adducts of copper(II) terephthalate
Complexes [(Cu(tpa)).H2O]n A (gauss) A (gauss) g 2.22 g 2.07 giso 2.12 2Cu G

58 60 61 62 64

3.14

[Cu(en)2]tpa.2H2O

190

53.33

2.23

2.02

2.09

0.8029

11.5

[Cu(bipy)2(H2O)2]tpa.4.H2O

160

46.66

2.27

2.04

2.12

0.7683

6.75

[Cu(phen)2(H2O)2]tpa.H2O

150

50

2.29

2.04

2.12

0.7605

7.25

[Cu(pn)(tpa)]n

2.18

2.07

2.11

2.57

9.3.6 Thermal decomposition features of copper terephthalates and their adducts

The thermal characterisation of copper(II) terephthalates and their adducts developed were carried out to study the ligation characteristics of the Lewis-bases and the over all decomposition features and also to evaluate their thermodynamic and kinetic parameters. The details are discussed below.
9.3.6.1 Phenomenological Aspects

(a)

[(Cu(tpa)).H2O]n, 58 The decomposition of [(Cu(tpa)).H2O]n is seen to be starting at 400C (Ti) and

progressing till 900C (Tf) with a peak temperature of 600C (Ts). The weight loss corresponding to this stage amounts to 7.4% which is in close agreement with the calculated value of 7.3% for the loss of a mole of lattice water. The second stage is seen commencing only at 2700C (Ti) and ending at 4000C (Tf) with a Ts of 3200C. The mass loss corresponding to this stage was found to be 60.15% agreeing well with the decomposition of [Cu(tpa)] unit to yield the final product of CuO (expected : 60.28%).

420

Chapter 9

Above

4000C,

the residue was seen to be stable. The decomposition features are

summarized below and the data are tabulated in Table 9.9. The amount of final residue of CuO obtained (32.45%) also confirms the initial stoichiometry and the nature of thermal steps given in eqns 9.1 and 9.2.

[(Cu(tpa)).H2O]n

, N2 40 - 900C
, N2

[Cu(tpa)]n + H2O

(9.1)

[Cu(tpa)]n

270 - 400 C

CuO + gaseous products.(9.2)

Table 9.9 The thermal characteristics of [(Cu(tpa)).H2O]n

Temp range (0C) 40-90 [(Cu(tpa)).H2O]n 270-400 Above 400 Peak temp. (0C) 60 320 Weight loss (in %) Found I II 7.40 60.15 32.45 (residue) Calcd 7.33 60.28 32.39 (residue) Probable reaction eq 9.1 eq 9.2 CuO

Compound

Stages

(b)

[Cu(en)2]tpa.2H2O, 60 The thermogram of en adduct is given in Fig.9.4. The decomposition is seen

initiating at 650C (Ti) and progressing till 1050C (Tf). The peak temperature was found to be 800C (Ts). The loss in mass observed for this decomposition stage amounts to 9.57% indicating the loss of two moles of lattice water (expected 9.38%). The second stage is seen operating at 1050C (Ti) itself and ending at 2700C (Tf) with a mass loss of 31.20%. This agrees well with the loss of two molecules of en from the complex (expected : 31.29%). The third stage of decomposition is seen initiating immediately at 2700C and ending at 4300C. This stage is attributed to the decomposition of [Cu(tpa)]n to the final residue of CuO. The mass loss calculated (38.59%) matches well with the observed value of 38.72%. The mass of the final residue was found to be 20.51% which is in close agreement with the theoretical value of 20.74%. The decomposition features are summarised below and the data are tabulated in Table 9.10.

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates

421

Fig 9.4 The thermogram (TG /DTG) of [Cu(en)2]tpa.2H2O in N2

[Cu(en)2]tpa.2H2O

, N2 65 - 105 C
0

[Cu(en)2]tpa + 2 H2O ....... (9.3)

[Cu(en)2]tpa

, N2 105 - 270 oC

[Cu(tpa)]n + 2 en ....................... (9.4)

[Cu(tpa)]n

, N2 270 - 430 oC

CuO + gaseous products .............. (9.5)

Table 9.10 The thermal characteristics of [Cu(en)2]tpa.2H2O

Temp range (0C) 65-105 105-270 [Cu(en)2]tpa.2H2O 270-430 Above 430 Peak temp (0C) 80 245 303 Weight loss (in %) Stages Found I II III 9.57 31.20 38.72 20.51 (residue) Calcd 9.38 31.29 38.59 20.74 (residue) Probable reaction eq 9.3 eq 9.4 eq 9.5 CuO

Compound

(c)

[Cu(bipy)2(H2O)2)]tpa.4H2O, 61

422

Chapter 9

Fig 9.5. gives the thermogram of the adduct. It shows a four stage decomposition pattern starting from 400C and ending at 4200C. The first stage was observed in the range 40-900C while the second stage was seen in the range 90-1150C. The third and fourth stages were found to be in the ranges 115-2700C and 270-4200C respectively. During the first stage the loss of four molecules of lattice water was seen to be taking place. The mass loss corresponding to this stage was found to be 11.15% which is in close agreement with the calculated value of 11.11% for the water loss. The second stage can be attributed to the loss of two moles of coordinated water from the adduct. The mass loss corresponding to this stage was found to be 5.55% which is in perfect match with the calculated value of 5.56%. In the third stage the observed weight loss (23.98%) was in agreement with the escape of one mole of bipy from the adduct (calculated value : 24.11%). In the fourth stage the loss of the remaining bipy moiety together with the decomposition of tpa moiety takes place to yield CuO as the final product. The mass loss corresponding to this stage was observed to be 47.10% agreeing well with the theoretical value of 46.94%. Above 4200C, a residue (CuO) was formed which was seen stable even at higher temperature. The mass of this residue was found to be 12.22% which was also in good agreement with the expected value of 12.28%. The decomposition features are summarized below and the relevant data are tabulated in Table 9.11.

Fig 9.5. The thermogram (TG/DTG) of [Cu(bipy)2(H2O)2)]tpa.4H2O in N2

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates , N2 [Cu(bipy)2(H2O)2)]tpa.4H2O [Cu(bipy)2(H2O)2]tpa + 4 H2O ..(9.6) 0 40 - 90 C

423

[Cu(bipy)2(H2O)2]tpa

, N2 90-115 C
, N2
0

[Cu(bipy)2]tpa + 2H2O ......(9.7)

[Cu(bipy)2]tpa

[Cu(bipy)(tpa)]n + bipy .............(9.8)

115-270 C

[Cu(bipy)(tpa)]n

, N2

270 - 420 C

CuO + bipy + gaseous products...(9.9)

424

Chapter 9

Table 9.11 The thermal characteristics of [Cu(bipy)2(H2O)2)]tpa.4H2O

Temp range (0C) 40-90 [Cu(bipy)2 (H2O)2)]tpa.4H2O 90-115 115-270 270-420 Above 420 Peak temp (0C) 50 110 195 278 Weight loss (in %] Found I II III IV 11.15 5.55 23.98 47.10 12.22 (residue) Calcd 11.11 5.56 24.11 46.94 12.28 (residue) Probable reaction Eqn 9.6 Eqn 9.7 Eqn 9.8 Eqn.9.9 CuO

Compound

Stages

(d)

[Cu(phen)2(H2O)2]tpa.H2O, 62 The thermogram of the adduct is given in Fig. 9.6. The initial decomposition

starts at 400C and progresses till 800C with a peak temperature of 500C (Ts). The loss in mass corresponding to this decomposition stage amounts to 2.80% which is in close agreement with the calculated value of 2.65% for the loss of a mole of lattice water. The second stage is seen operating at 800C and ending at 1700C with a peak temperature of 1300C. The loss in mass during this stage amounts to The third stage commences at 1700C and 5.45% which is in close agreement with the theoretical value of 5.31% for the loss of two moles of coordinated water. progresses till 2800C with a peak temperature of 2550C. The weight loss observed at this stage can be attributed to the loss of one mole of phen moiety from the adduct (found: 29.3%; expected : 29.2%). The fourth stage starts at 2800C and ends at 8400C, with a mass loss of 50.65%. In this stage the escape of the remaining phen moiety together with the decomposition of tpa moiety can be expected to take place to yield CuO as the final product. Above 8400C, the residue was seen to be stable in the nitrogen atmosphere. The values are tabulated in Table 9.12 and the reactions involved are given below.

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates

425

Fig. 9.6 The thermogram (TG/DTG) of [Cu(phen)2(H2O)2]tpa.H2O in N2

[Cu(phen)2(H2O)2]tpa. H2O

, N2 40 - 80 C

[Cu(phen)2(H2O)2]tpa + H2O ..(9.10)

[Cu(phen)2(H2O)2]tpa

, N2 80-170 C

[Cu(phen)2]tpa + 2H2O ........... (9.11)

[Cu(phen)2]tpa

, N2 170-280 C

[Cu(phen)(tpa)]n + phen ................... (9.12)

[Cu(phen)(tpa)]n

, N2 280-840 C

CuO + phen + gaseous products . (9.13)

426

Chapter 9

Table 9.12 Thermal decomposition features of [Cu(phen)2(H2O)2]tpa.H2O

Temp range (0C) 40-80 80-170 [Cu(phen)2(H2O)2] tpa. H2O 170-280 280-840 Above 840 Peak temp (0C) 45 130 255 550 Weight loss (in %) Stages Found I II III IV 2.80 5.45 29.30 50.65 11.80 (residue) Calcd 2.65 5.31 29.24 51.07 11.73 (residue) Probable reaction eq 9.10 eq 9.11 eq 9.12 eq 9.13 CuO

Compound

(e)

[Cu(py)2(tpa)]n, 63 The thermogram of the adduct is shown in Fig 9.7. It is seen to be thermally

stable upto 1700C indicated by a well defined plateau. The decomposition is seen starting at 1700C (Ti) and gradually progressing till 3150C (Tf). The weight loss corresponding to the stage amounts to 40.53% which indicates the loss of two moles of py from the compound (expected : 41.01%). The second stage of decomposition is seen commencing at 3150C and ending at 4030C with a mass loss of 38.25%. This stage could be attributed to the decomposition of tpa moiety from [Cu(tpa)]n to yield CuO. The residual mass of 21.22% agrees well with the theoretical value of 20.62%.

Fig. 9.7 The thermogram (TG/DTG) of [Cu(py)2(tpa)]n in N2

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates

427

The decomposition features are summarized below and the data tabulated in Table 9.13.
, N2 o 170 - 310 C

are

[Cu(py)2(tpa)]n

[Cu(tpa)]n + 2py ........................(9.14)

[Cu(tpa)]n

, N2 o 310 - 405 C

CuO + gaseous products .................(9.15)

Table 9.13 Thermal characteristics of [Cu(py)2(tpa)]n

Temp range (0C) 170-310 [Cu(py)2(tpa)]n 310-405 Above 405 Peak temp (0C) 218 325 Weight loss (in %) Found I II 40.53 38.25 21.22 (residue) Calcd 41.01 38.37 20.62 (residue) Probable reaction eq 9.14 eq 9.15 CuO

Compound

Stages

428

Chapter 9

(f)

[Cu(pn)(tpa)]n, 64 The thermogram of the adduct is shown in Fig 9.8. This compound is seen to

be stable upto 2150C indicated by a well defined horizontal plateau in the TG curve. It shows only one decomposition stage. The weight loss is seen starting at 2150C and ending at 3950C with a peak temperature of 2850C. The loss in mass corresponding to this stage was found to be 73.55% which was in perfect match with the theoretical value of 73.63% expected for the decomposition of the compound to a final product of CuO. The decomposition features are given in Table 9.14.

Fig. 9.8: The thermogram (TG/DTG) of [Cu(pn)(tpa)]n in N2

[Cu(pn)(tpa)]n

, N2 215 - 395 C
0

CuO + pn + gaseous products ...(9.16)

Table 9.14 Thermal characteristics of [Cu(pn)(tpa)]n in N2

Compound Temp range (0C) 215-395 [Cu(pn)(tpa)]n Above 395 Peak temp (0C) 285 Stages I Weight loss (in %) Found 73.55 26.45 (residue) Calcd 73.63 26.37 (residue) Probable reaction eq 9.16 CuO

9.3.6.2 Kinetic and Mechanistic Aspects The overall kinetics and the nature of mechanisms of thermal decomposition of various Lewis-base adducts of copper(II) terephthalate were studied using non-

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates

429

isothermal thermogravimetric techniques. Kinetic parameters for all the complexes at various stages were calculated from the TG/DTG curves using Coats-Redfern method.(47) The deduction of the possible mechanisms of reactions from nonisothermal methods has been discussed by Sestak and Berggren.(48) From the nine reaction mechanisms listed by Satava, the one which gives the best representation of the experimental data is considered as the mechanism of the reaction. Linear plots (Fig. 9.9) of nine forms of g()/T2 versus 103/T were drawn by the least square method and the corresponding correlation coefficients were evaluated. The data are presented later in Tables 9.16-9.19. The values of Ea and A were calculated in each case from the slope and intercept respectively. The kinetic parameters evaluated for different stages of decompositions of the adducts using nonmechanistic equation are given in Table 9.15.

430

Chapter 9

-7.5

Lewis-base adducts of [(Cu(tpa)).H2O]n

Stage I

-8.0

Lewis-base adducts of [(Cu(tpa)).H2O]n

Stage II

-8.0

-8.5

log (g()/T )

log (g()/T )

c
-8.5

b
-9.0

b
-9.0

-9.5

d e
-9.5 1.8 2.0 2.2 2.4 2.6 2.8 -10.0

c d

a
3.0 3.2 1.2 1.4 1.6

1.8

2.0

2.2

2.4

2.6

1000/T

1000/T

(i)

(ii)

-7.5

Lewis-base adducts of [(Cu(tpa)).H2O]n

Stage III

-7.2 -7.6

StageIV

-8.0

-8.0 -8.4

log (g()/T )
2

log (g()/T )
2

-8.5

-8.8 -9.2 -9.6 -10.0

-9.0

c
Lewis base adducts of [(Cu(tpa)).H2O]n

-9.5

c a
1.5 1.6 1.7 1.8 1.9 2.0 2.1

-10.4 -10.8 1.0 1.2

1.4

1.6

1.8

2.0

1000/T

1000/T

(iii)

(iv)

Fig 9.9 Log (g()/T2) Vs 1000/T plots for the thermal decomposition of Lewis-base adducts of [(Cu(tpa)).H2O]n 58 : [Cu(en)2]tpa.2H2O 60 (i) Stage I (ii) Stage II (iii) Stage III and (iv) Stage IV; (a) (b) [Cu(bipy)2(H2O)2]tpa.4H2O 61 (c)

[Cu(phen)2(H2O)2]tpa.H2O 62 (d) [Cu(py)2(tpa)]n 63 (e) [Cu(pn)(tpa)]n 64

Table 9.15

Kinetic parameters for the thermal decomposition stages of Lewis-base adducts of copper(II) terephthalate
Kinetic parameters Compounds [Cu(en)2]tpa. 2H2O 60 89.19 148.31 -204.78 45.86 0.034 -277.27 66.15 0.05 -275.39 [Cu(bipy)2(H2O)2]tpa. 4H2O 61 99.72 4595.62 -175.54 42.05 5.29 10-2 -272.78 137.08 1031.39 -191.92 145.00 925.05 -186.25 [Cu(phen)2(H2O)2]tpa.H2O 62 36.03 7.39 10-2 -267.22 53.86 6.82 10-2 -269.89 60.09 6.44 10-2 -272.39 76.92 6.42 10-3 -295.37 [Cu(py)2(tpa)]n 63 46.04 2.30 10-2 -280.32 141.59 44.88 -219.07 [Cu(pn) (tpa)]n 64 117.85 39.71 -219.30 -

Stages

Ea(kJ/mol) I A(s-1) S(J/K/mol) Ea(kJ/mol) II A(s-1) S (J/K/mol) Ea(kJ/mol) III A(s-1) S (J/K/mol) Ea(kJ/mol) IV A(s-1) S (J/K/mol)

432

Table 9.16

Correlation coefficients calculated using the nine form of g() for the Lewis-base adducts of [(Cu(tpa)).H2O]n for stage I decomposition
[Cu(en)2 ] tpa.2H2O 60 -0.996092 -0.996072 -0.994724 -0.996116 -0.995709 -0.994121 -0.992121 -0.995597 -0.995604 [Cu(bipy)2(H2O)2]tpa. 4H2O 61 -0.991839 -0.991784 -0.989723 -0.991886 -0.990885 -0.988119 -0.985247 -0.990854 -0.990788 [Cu(phen)2(H2O)2]tpa. H2O 62 -0.995533 -0.995538 -0.991202 -0.995624 -0.993812 -0.985968 -0.952098 -0.994069 -0.993964 [Cu(py)2 tpa]n 63 -0.992829 -0.993178 -0.979397 -0.993271 -0.990182 -0.967564 --0.721182 -0.989399 -0.989649 [Cu(pn) (tpa)]n 64 -0.991897 -0.992207 -0.988617 -0.992360 -0.991579 -0.987958 -0.981863 -0.991001 -0.991098

Form of g() 2 +(1-) ln(1-) [1-(1-)1/3]2 (12 3

)-(1-)2/3

-ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3

433

Table 9.17 Correlation coefficients calculated using the nine forms of g() for the Lewis-base adducts of [(Cu(tpa)).H2O]n for stage II decomposition
Form of g() [Cu(en)2 ]tpa.2H2O

60

[Cu(bipy)2(H2O)2]tpa.4H2O

61

[Cu(phen)2(H2O)2]tpa.H2O

62

[Cu(py)2(tpa)]n

63

2 +(1-) ln(1-) [1-(1-)1/3]2

2/3 (1- 2 3 )-(1-)

-0.989798 -0.990225 -0.975033 -0.990338 -0.986698 -0.963666 -0.806296 -0.985724 -0.986085

-0.992095 -0.992502 -0.981251 -0.992638 -0.990212 -0.972485 -0.866578 -0.989265 -0.989543

-0.996454 -0.996472 -0.992878 -0.996509 -0.995262 -0.990353 -0.965769 -0.995181 -0.995330

-0.985050 -0.985339 -0.979116 -0.985454 -0.983609 -0.976730 -0.965757 -0.983077 -0.983222

-ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3

434

Table: 9.18 Correlation coefficients calculated using the nine forms of g() for the Lewis-base adducts of [(Cu(tpa)) (H2O)]n for Stage III decomposition
Form of g() 2 +(1-) ln(1-) [1-(1-)1/3]2
2/3 (1- 2 3 )-(1-)

[Cu(en)2 ]tpa.2H2O

60

[Cu(bipy)2(H2O)2]tpa.4H2O

61

[Cu(phen)2(H2O)2]tpa.H2O

62

-0.993592 -0.993901 -0.984473 -0.993954 -0.991715 -0.977-066 -0.892917 -0.991025 -0.991304

-0.988623 -0.988693 -0.986172 -0.989101 -0.986498 -0.982603 -0.976777 -0.987146 -0.886975

-0.984442 -0.985377 -0.962589 -0.985701 -0.981114 -0.950455 -0.790610 -0.979049 -0.979817

-ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates

435

Table. 9.19. Correlation coefficients calculated using the nine forms of g() for the Lewis-base adducts of [(Cu(tpa)).H2O]n for Stage IV decomposition
Form of g() 2 +(1-) ln(1-) [1-(1-)1/3]2
2/3 (1- 2 3 )-(1-)

[Cu(bipy)2(H2O)2]tpa.4H2O

61

[Cu(phen)2(H2O)2]tpa.H2O

62

-0.980421 -0.993492 -0.987253 -0.994789 -0.992042 -0.987926 -0.983520 -0.991325 -0.982762

-0.990543 -0.990613 -0.973829 -0.990686 -0.925616 -0.950408 -0.453627 -0.985219 -0.985340

-ln(1-) [-ln(1-)]1/2 [-ln(1-)]1/3 1-(1-)1/2 1-(1-)1/3

The activation energies, Ea, in the first stage of thermal decomposition of the Lewis base adducts of copper(II) terephthalate were in the range 36-118 kJ/mol, but that of second, third and fourth stages of decompositions are in the range 42-142 kJ/mol, 60-137 kJ/mol and 77-145 kJ/mol respectively. The pre-exponential factors A vary in a wide ranges of values as 2.3010-2 - 4596 s-1 for the first stage, 0.034-44.88 s-1 for the second stage, 0.05-1031 s-1 for the third stage and 6.4210-3 -925 s-1 for the fourth stage of decompositions. The S values are in the ranges -176 to -1280 J/K/mol, -219 to -277 J/K/mol, -192 to -275 J/K/mol

436

Chapter 9

and -186 to -295 J/K/mol respectively for these stages. The negative values indicate that the activated complexes for all the stages of decomposition have a more ordered structure than the reactants and the reactions in these cases, may be described as slower than the normal.(49-51) However, no definite trend is seen in the values of Ea or S for the various stages of thermal decomposition of the same complex. From the correlation coefficients obtained from the kinetic studies (Tables 9.16-9.19) it is evident that the rate controlling process for all the four stages of decompositions is three dimensional diffusion, spherical symmetry; obeying Ginstling Brownshtein equation. The forms of g() with the highest value of correlation coefficient for all the stages of thermal decomposition of the complexes are given in Table 9.20.

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates

437

Table 9.20 The form of g() with the highest value of correlation coefficients and the corresponding rate controlling processes
Stages Compound Form of g() Rate controlling process Three dimensional diffusion, spherical symmetry, GinstlingBrownshtein equation

[Cu(en)2]tpa.2H2O

(1-2/3) (1-2)3/2

[Cu(bipy)2(H2O)2]tpa.4H2O [Cu(phen)2(H2O)2]tpa.H2O [Cu(py)2(tpa)]n [Cu(pn)(tpa)]n [Cu(en)2]tpa.2H2O [Cu(bipy)2(H2O)2]tpa.4H2O

(1-2/3) (1-2)3/2 (1-2/3) (1-2)3/2 (1-2/3) (1-2)3/2 (1-2/3) (1-2)3/2 (1-2/3) (1-2)3/2 (1-2/3) (1-2)3/2 (1-2/3) (1-2)3/2 (1-2/3) (1-2)3/2 (1-2/3) (1-2)3/2 (1-2/3) (1-2)3/2 (1-2/3) (1-2)3/2 (1-2/3) (1-2)3/2 (1-2/3) (1-2)3/2

II [Cu(phen)2(H2O)2]tpa.H2O [Cu(py)2(tpa)]n [Cu(en)2]tpa.2H2O III [Cu(bipy)2(H2O)2]tpa.4H2O [Cu(phen)2(H2O)2]tpa.H2O [Cu(bipy)2(H2O)2]tpa.4H2O IV [Cu(phen)2(H2O)2]tpa.H2O

438

Chapter 9

Reference 1. 2. 3. 4. 5. 6. 7. 8. J. Rogan, D. Poleti, L. J. Karanovic, G. Bogdanovic and D. M. Petrovic, Polyhedron; 19 (2000) 1415 L. Deakin, A. M. Arif and J. G. Miller, Inorg. Chem; 38 (1999) 5072 M. Kurmoo, H. Kumagai, M. A.Green, B. W. Lovett, A. Ardavan and J. Singleton, J. Solid State Chem; 159 (2001) 343 S. H. Dale and M. R. J. Elsegood, Acta Cryst; C59 (2003) m475 S. M. F. Lo, S. S. Y. Chui and I. D. Williams, Acta Cryst; C54 (1998) 1846 Z. L. Huang, M. Drillon, A. Sironi, J. T. Zhao, P. Rabu and P. Panissod, Chem. Mater; 12 (2000) 2805 J. A. Kaduk, Acta Cryst; B58 (2000) 815 (a) W. Mori, K. Yoshida, H. Nakayama, S. Takamizawa and N. Kishita, Chem. Letters; (1997) 1219 (b) B. W. Lovett, H. Kumagai and M. Kurmoo, Synthe. Metals; 121 (2001) 1814 (c) K. Seki, S. Takamizawa and W. Mori, Chem. Lett; (2001) 122 9. 10. 11. 12. 13. S. H. Dale, M. R. J. Elsegood and S. Kainth, Acta Cryst; C60 (2004) m76 L. C. Li, D. Z. Liao, Z. H. Jiang and S. P. Yan, Polyhedron; 20 (2001) 681 L. C. Li, D. Z. Liao, Z. H. Jiang and S. P. Yan, J. Mole. Struc; 597 (2001) 157 D. F. Sun, R. Cao, Y. C. Liang, Q. Shi, W. P. Su and M. C. Hong, J. Chem. Soc. Dalton Trans; (2001) 2335 P. H. Groeneman, L. R. M. Gillivray and J. L. Atwood, Inorg. Chem; 38 (1999) 208

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates

439

14. 15. 16. 17. 18. 19. 20. 21. 22. 23.

F. Chem, X. H. Li, H. P. Xiao and M. L. Hu, Acta Cryst; E60 (2004), m708 X. H. Li and H. P. Xiao, Acta Cryst; E60 (2004) m898 H. P. Xiao and L. G. Zhu, Acta Cryst; E59 (2003) m964 Y. W. Li, H. Xiang, T. B. Lu and S. W. Ng, Acta Cryst; E60 (2004) m317 Y. L. Fu, J. L. Ren, H. P. Qiao and S. W. Ng, Acta Cryst; E60 (2004) m1510 H. L. Zhu, Z. G. Wang, Y. S. Lin and Y. Zou, Acta Cryst; E59 (2003) m942 C. M. Zakaria, G. Ferguson, A. J. Lough and C. Glidewell, Acta Cryst; C57 (2001) 683 H. P. Xiao, M. L. Hu and X. H. Li, Acta Cryat; E60 (2004) m336 H. P. Xiao, X. H. Li, M. D. Ye and M. L. Hu, Acta Cryst; E60 (2004) m253 (a) Y. T. Li, C. W. Yan and D. Z. Liao, Synth. React. Inorg. Met. Org. Chem; 29 (1999) 155 (b) Y. T. Li, C. W. Yan and D, Z. Liao, Trans. Met. Chem; 23 (1998) 237

24.

(a) H. L. Zhu, Y. X. Tong, X. M. Chen and C. X. Ren, Trans. Met. Chem; 26 (2001) 528 (b) I. Z. Zou, Y. Wu, C. Y. Duan, Y. J. Liu, Z. Xu, Trans. Met. Chem; 23 (1998) 305 (c) J. Cano, G. D. Munno, j. L. Sanz, R. Ruiz, J. Faus and M. Julve, J. Chem. Soc. Dalton Trans; (1997) 1915 (d) D. Sun, R. Cao, Y. Liang, M. Hong, W. Su and J. Weng, Acta Cryst; C56 (2000) e240

25.

J. Rogan, D. Poleti and L. Karanovic, J. Serb. Chem. Soc; 69(5) (2004) 353

440

Chapter 9

26. 27.

J. Cano, G. D. Munno, J. L. Sanz, R. Ruiz, j. Faus and M. Julve, J. Chem. Soc. Dalton Trans; (1994) 3465 (a) J. M. Shi, D. Z. Liao, Z. H. Jiang and G. L. Wang, Polish J. Chem; 69 (1995) 346 (b) M. M. Miao, D. Z. Liao, Z. H. Jian, P. Cheng and G. L. Wang, Trans. Met. Chem; 22 (1997) 39

28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39.

H. Q. Zeng, M. Yang, X. Y. Huang and X. Y. Chen, Cryst. Resear. Tech; 32 (1997) 467 Y. Liu, D. J. Xu and J. G. Liu, J. Coord. Chem; 54 (2001) 175 H. P. Xiao, Z. Shi, L. G. Zhu, R. R. Xu and W. Q. Pang, Acta Cryst; C59 (2003) m82 H. P. Xiao, Z. Shi, L. G. Zhu, R. R. Xu and W. Q. Pang, Acta Cryst; E60 (2004) m209 O. Z. Zhang and C. Z. Lu, Acta Cryst ; E60 (2004) m1289 C. X. Zhang, F. Chen, C. B. Ma, M. Q. Hu, C. N. Chen and Q. T. Liu, Acta Cryst; C60 (2004) m288 H. Li, M. Eddaoudi, M. O Keeffe, O. M. Yaghi, Nature; 402 (1999) 276 Vogels Text Book of Practical Organic Chemistry; IVth Ed. ELBS, London (1978) G. B. Deacon and R. Philips, Coord. Chem. Rev; 88 (1980) 227 R. S. Drago, Physical Methods in Chemistry Saunders, Philadelphia (1969) A. B. P. Lever Inorganic Electronic Spectroscopy, 2nd Ed, Elsevier, Amsterdam, 1984 R. H. Holm and M. J. O Connor, Prog. Inorg. Chem; 14 (1971) 241

Interaction of Lewis-bases with Polymeric Metal(II) Terephthalates

441

40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 51.

F. A Cotton and J. J. Wise, Inorg. Chem; 6 (1967) 917 J. A. Dean Langes Hand Book of Chemistry 13th Ed, Mcgrew Hill Book 43. Company, New York (1972) 5.18-5.60 Y. Nishida and S. Kida, Coord. Chem. Rev; 15 (1975) 279 M. A. Hitchman, T. D. Waite, Inorg.Chem; 15 (1976) 2150 M. R. G Nair and C. P Prabhakaran J. Inorg. Nucl. Chem; 43 (1981) 3390 B. Singh. B. P. Yadava and R. C. Aggarwal. Indian. J. Chem; 23 A (1984) 441 M. Shakir, S. Islam, A. K. Mohamed, N. Jahan, Trans. Met. Chem; 22 (1996) 189 A. W. Coats and J. P. Redfern, Nature; 201 (1964) 68 J. Sestak and G. Berggren, Thermochim. Acta; 3 (1971) 1 A. A. Froast and R. G. Pearson, Kinetics and Mechanism, Wiley, New York, (1961) T. Gangadevi, K. Muraleedharan and M. P. Kannan, Thermochim. Acta; 146 (1989) 225 K. K. Aravindakshan and K. Muraleedharan; Thermochim. Acta, 155 (1989) 247

Chapter 10 Summary and Conclusion

compositionally well defined fragments which are expected to have interesting framework structures. The dicarboxylic acids chosen are succinic acid (H 2 suc), malonic acid (H 2 mal), 1,4-benzene dicarboxylic acid (H 2 tpa) and oxalic acid (H 2 ox) having -CH 2 CH 2 -, -CH 2 -, phenylene respectively as spacer group for the first three and no spacer for the oxalic acid. The selection is made such that we get systems with both flexible and rigid functions. We confined our studies mostly to nickel(II), cobalt(II) and copper(II) ions. A wide variety of analytically pure mixedligand complexes also could be isolated by employing different reaction conditions. The Lewis-bases selected for study are ethylenediamine (en), 2,2'-bipyridyl (bipy), 1,10-phenanthroline (phen), 1,3-diaminopropane (pn) and pyridine (py) which are either chelating, conjugatively chelating or monodentate in nature so that the systems with variety of structural features could be generated. Detailed structural and electronic characterisation were carried out by spectral and other analytical techniques. Some of the adducts could be crystallized and single-crystal XRD study carried out to determine their crystal and molecular structures. The thermal behaviour of various adducts developed have also been studied in some detail to look into the phenomenological, kinetic and mechanistic aspects involved in them. Some of the mixed ligand complexes isolated are seen to have interesting thermal decomposition features.

olymeric metal dicarboxylate complexes having various spacer moieties between the two carboxyl functions are synthesized and a systematic study carried out to generate

446

Chapter 10

The thesis is presented in 10 chapters. In Chapter 1 is given an overview of some of mono- and dicarboxylates in general and their interesting bonding features along with their relevance in biological systems and application in various aspects. It also discusses the scope and objectives of the present work in brief. In Chapter 2 is given the reagents and methods employed along with the theoretical principles involved in both kinetic and mechanistic aspects of the thermal decomposition of various products isolated. Some basic aspects of Ni(II), Co(II) and Cu(II) systems in general are also included in this chapter. Chapter 3 discusses the preparation and characterisation of metal succinates which are polymeric in nature. The interaction of Lewis-bases with nickel(II), cobalt(II) and copper(II) succinates in various conditions are studied in detail. Various Lewis-base adducts thus generated are characterised by analytical, spectroscopic and magnetic measurements. The bonding features of the resulting mixed ligand complexes are also deduced from the data. An attempt was made to correlate the trend observed in various spectroscopic parameters (Dq, and B) with the nature and extent of the Lewis-bases present in them. A distinct perceptible change in these parameters are seen between monomeric and their polymeric species. The crystal and molecular structure of phen adduct of copper(II) succinate grown as single crystal could also be carried out. The dimeric nature of the complex with [Cu2(phen)4(suc)]2+ cation and having isolated succinate dianion H-bonded with water molecules is seen to have interesting stacking features. These are also discussed in this chapter.

Summary and Conclusion

447

In Chapter 4 is discussed the detailed thermal decomposition features of metal succinates and their various Lewis-base adducts developed. The thermograms of certain adducts in this system show the loss of Lewis-bases in a single step in the early stages yielding the parent metal succinate while some others show the loss of Lewis-bases in the initial step followed by the combined decomposition of the remaining products. The phenomenological aspects of the decomposition features of the adducts and various thermodynamic parameters associated with the thermal steps are evaluated by Coats-Redfern method and discussed in this chapter. The possible mechanisms involved could also be suggested. In Chapter 5 is given the preparation of various metal malonates and generation of several mixed ligand complexes with varying compositions by interaction with varieties of Lewis-bases in various conditions and stoichiometry. The structural and electronic characterisation of the adducts generated are carried out by spectral and magnetic measurements and results discussed. The crystal and molecular structure of bipy adduct of copper(II) malonate grown as single crystal could also be carried out. The Cu atom is seen to be bonded to malonate group through chelation involving single oxygen of each of the two carboxyl groups of malonate moiety forming a six-membered ring. The structure is seen to be consisting of a one-dimensional copper(II) complex resulting from mononuclear mixed ligand copper(II) fragments via hydrogen bonds. The Cu atom is five coordinate in a distorted square pyramidal environment. The crystal is seen to have interesting stacking properties. These are also discussed.

448

Chapter 10

The

thermal

decomposition

characteristics

of

metal

malonates and their various Lewis-base adducts are discussed in Chapter 6. The thermograms of certain adducts in this system show the loss of Lewis-base in the initial step followed by the combined decomposition of the remaining products. Most of the adducts show only a cumulative decomposition involving Lewisbases and mal moieties. However, certain other adducts show the loss of Lewis-bases in early stage in a step, yielding back the parent complex. The phenomenological aspects of the thermal decompositions are studied and the evaluation of thermodynamic and kinetic parameters are carried out and discussed in this chapter. In Chapter 7 is discussed the preparation of various metal oxalates by adopting different synthetic routes. metal succinates or metal malonates. These polymeric metal oxalates are seen to be more rigid than the corresponding They are characterised by Unlike the spectroscopic, analytical and magnetic studies.

succinate and malonate systems we see that Lewis-base attack does not yield any ionic fragments but results in the generation of only polymeric adducts. Structural and electronic properties of various adducts isolated are discussed. The thermal decomposition characteristics of metal oxalates and their various Lewis-base adducts are discussed in Chapter 8. It shows stepwise dissociation in most of the Lewis-base adducts of oxalate complexes. However, certain adducts show only cumulative decomposition. As in the other systems, the phenomenological aspects are studied and their various kinetic and thermodynamic parameters are evaluated.

Summary and Conclusion

449

The preparation of different metal terephthalates by adopting various synthetic routes are discussed in Chapter 9. The interaction of Lewis-bases with the polymeric metal terephthalates could be studied in various conditions. The characterisation of the various adducts generated was carried out by analytical, spectroscopic and magnetic studies. The thermograms of certain adducts in this system show the loss of Lewis-bases in a single step yielding the parent complex while certain other adducts show the loss of Lewis-bases in a single step followed by the combined decomposition. The phenomenological aspects were analysed and the kinetic and thermodynamic parameters were evaluated for the various decomposition steps of the adducts. Several interesting features could be observed in the adducts formation by the Lewis-base interaction with metal dicarboxylates. We could see that some of the Lewis-bases affect the fragmentation of polymeric dicarboxylates in a facile manner to generate monomeric mixed ligand complexes while some others, after breaking up the polymeric chain, try to regenerate a different variety of coordination polymers by incorporating Lewis-bases. Yet another variety (mostly oxalates) try to keep the original polymeric network but incorporate Lewis-bases in the available coordination sites. While Lewis-bases have the expected Dq values based on the spectrochemical series, we find that the effective Dq values (also and B) of the Lewis-bases in the mixed ligand complexes depend largely on the nature and the way in which the carboxylate function of the acid moiety linked to the metal ion. This is mainly due to the synergetic effect caused by both the Lewis-bases and carboxylate functions through the -donor and -acceptor abilities.

450

Chapter 10

Since it was difficult for us to grow suitable single crystals for most of the adducts, we had to resort to the available spectroscopic techniques to identify the nature of bonding and the structure of Lewis-base adducts. The asymmetric and symmetric (COO-) stretching

frequencies of carboxylate moieties could be used as finger prints to identify the bonding nature of the -COO- group and also to infer the overall structure of the complexes. Further, it was also instructive to see the change in of these carboxylate bands depending on both the nature of metal ion and also the ligated Lewisbases. A considerable extent of modulation is seen to be taking place in the carboxylate moiety because of the back-donation from the metal ion. The back-donation from the metal to the carboxylate * orbitals seems to be augmented largely by the -donor ability of the coordinated Lewis-bases and also marginally on their -acceptor properties. Eventhough EPR spectra of soluble copper(II) dicarboxylates and their adducts could be analysed for getting some useful information on their electronic features, the polymeric and insoluble nature of other products prevented us from extracting useful information. Most of the resolved spectra could be analysed by assuming an almost axial symmetry for the complexes. A dx2-y2 ground state is consistently seen in all of them. Considerable variations seen in A values indicate that appreciable delocalisation of spin takes place spanning the coordinated ligands. Both the coordinated carboxylate moiety and Lewis-bases are seen to augment this delocalisation. The evaluated -covalency factor 2 is

Summary and Conclusion

451

also seen to be dependent on this synergetic feature. We have seen that both eff and EPR G parameter for the parent metal dicarboxylates are indicative of appreciable exchange interaction existing in them. But when the Lewis-base attack on the polymeric metal dicarboxylates leads to fragmentation resulting in monomeric mixed-ligand complexes we see that no such exchange interaction is manifested in them. However, when the Lewis-base adducts also retain polymeric nature, such exchange interaction is seen to persist. We have looked into the thermal dissociation features of both metal dicarboxylates and their Lewis-base adducts with a view to identify the possible intermediates involved. Eventhough the parent metal dicarboxylates thermally release water molecules, further dissociation seems to be always a single step reaction. In the case of Lewis-base adducts we do find, in most cases, stepwise loss of the N-bases yielding stable intermediates which themselves are interesting mixed ligand complexes. We have made some attempts to evaluate some of the thermodynamic parameters involved in such well characterised thermal steps. A considerable dependency of these parameters on the nature of the Lewis-bases, type of the metal and the dicarboxylate moiety is seen.