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The chelate complexes are more stable than similar complexes containing unidentate ligands. The greater
stability of the chelate complex in comparison to normal complex is called chelate effect. For example,
Ni2+ (aq) + 6 NH3 (aq) [Ni(NH3)6]2+ (aq) Kformation = 108
2+
Ni (aq) + 3 NH2CH2CH2NH2(aq) 2+
[Ni(en)3] (aq) Kformation = 1018
The five and six membered rings are more stable.
The following are type and examples if ligands on the basis of this classification.
(a) Monodentate (one donor atom) :
F, Cl, Bl, H O
2
: , N
H , CN , NO , OH, CO, NO, C H N (py) etc.
3 2 5 5
(b) Didentate (two donor atoms : Some most common bidentate ligands are
O O
C C
OR C2O42
O O
Oxalate ion (ox2-)
O O
C
CO32 OR || 2, 2 bipyridyl (bipy)
O
Carbonate ion
OR
OR
CH3 C N O
| OR
CH3 C N OH
DIDENTATE CHELATION :
In [PtCl2(en)], en represents the didentate ligand, NH2CH2CH2NH2 (1,2-ethanediamine or ethylenediamine)
[Figure]
H2
Cl N
CH2
Pt
N CH2
Cl
H2
[PtCl2(en)]
(a)
CH2
CH2
H2N
Pt NH CH2
Cl N NH
H2
+
[PtCl(dien)]
(b)
H2C CH2
H H
N N
H2C Pt CH2
H2C N N CH2
H2 H2
2+
[Pt (trien)]
(c)
O O 3
OCCH CH2CO
2
N(CH2 )2N
OCCH
2
H
or
O
(Ethelenediaminetriacetato ion)
This acid is directly not soluble in water but its sodium salt is soluble.
O O 4
: :
: :
:O C CH2 CH2 C O:
:N CH2 CH2 N: O
: :
: :
:O C CH2 CH2 C O: or
O O
EDTA4, Ethylenediaminetetraacetate ion
Therefore, acid is not the ligand but its tetra anion is a ligand and its usual denticity is 6 but it is sometimes
also found to behave as tetradentate ligand and hence is a flexidentate ligand.
RESONANCE COORDINATION COMPOUND - 5
(g) FLEXIDENTATE LIGAND :
A polydentate ligand which is found to have different denticity in different coordination compounds is called a
flexidentate ligand. Note that in a particular complex denticity of a particular ligand is fixed, it can not be
flexible in the same compound.
EDTA can act as hexa, penta as well as tetra dentate ligand. For example ;
EDTA usually acts as hexadentate ligand but in [Cr(III)(OH)(EDTA)]2 and [Co(III)Br(EDTA)]2 as pentadentate
and in [Pd(II)H2(EDTA)]0 as a tetradentate ligand.
Sulphate ion, SO42 can also be mono or bi dentate ligand. For example ;
nitrito-N
M ON=O nitrito-O
M SCN thiocyanato or thiocyanato-S
M NCS isothiocyanato or thiocyanato-N
acetylacetonato (acac)
o - phenanthroline (o-phen)
N.. ..N
urea
2, 2 bipyridyl (bipy)
Pb lead plumbate
Ag silver argentate
Au gold aurate
Sn tin stannate
Fe iron ferrate
Note : The name of central atom is not modified if the central atom is in the neutral part of the complex.
Tetraaquacobalt(III)amidohydroxidotetramminechromium(III) sulphate
Some other examples are
RESONANCE COORDINATION COMPOUND - 10
(ii)
(iii) (SO4)2
dihydroxidobis(tetraaquairon(III)) sulphate
(iv) (SO4)2
amidohydroxidobis(bis(ethylenediammine)cobalt(III)) sulphate
OR bis(ethylenediammine)cobalt(III)amidohydroxidobis(ethylenediammine)cobalt(III) sulphate.
Fe
The name of the above compund is bis(cyclopentadienyl)iron(II). This is commonly known as Ferrocene.
In the above compound the aromatic pi electron density of the ring is being donated to the Fe2+ ion, hence in
this way iron is bonded to all the five carbons of the upper flat ring and also to all five carbons of below flat ring.
This is also called a sandwich compound because of its shape. Its not a true complex this is an organome-
tallic compound which we study in detail in the last part of the chapter. To write down the formula of such
compound a special symbol is written before the name of such ligand and on superscript to this the
number of atoms is written between which the electron density is being shared. So the formula of this
compound will be Fe[ 5C5H5]2 .
The other such example is bis(benzene)chromium which will be represented by the formula
Cr[ 6C6H6]2
H H
C
Cl
Ti+4 C
Pt H H
Cl Cl
CN = 6 Octahedral
The secondary valencies are generally represented by solid lines while the primary valencies are represented
by dashed lines and the ions which satisfy both primary and secondary valencies will be drawn with both
solid and dashed lines. For example the complex [CoCl (H2O)5] Cl2 is represented as
On the basis of the above postulates, Werner formulated the coordination compounds, CoCl3 . 6NH3, CoCl3
. 5NH3 and CoCl3 . 5NH3 and CoCl3 . 4NH3 as : [Co(NH3)6]Cl3, [CoCl(NH3)5]Cl2 and [CoCl2(NH3)4]Cl.
respectively - the species within the square brackets being the coordination entitles (complexes) and the
ions outside the square brackets the counter ions. He further postulated that octahedral, square, planar and
tetrahedral geometrical shapes are more common in coordination compounds of transition metals. Thus,
[Co(NH3)6]3+, [CoCl(NH3)5]2+, [CoCl2(NH3)4]+ are octahedral entities, while [Ni(CO)4] and [PtCl4]2 are tetrahe-
dral and square-planar, respectively.
Series of coloured compounds obtained by the interaction of aqueous CoCl3 and NH3
Compound Colour Name according to colour
CoCl3 . 6NH3 Yellow Luteo Complex
CoCl3 . 5NH3 Purple Purpureo Complex
CoCl3 . 4NH3 Green Praseo Complex
CoCl3 . 4NH3 Violet Violeo Complex
RESONANCE COORDINATION COMPOUND - 12
Werner used some experimental methods to find out the number of free ions and coordination number in
many different complexes. Such methods involved freezing point dpression measurement or boiling
point elevation measurement of aqueous solution of these complexes( we will study later about these
methods). Other methods included conductivity measurement of the aqueous solutions of these com-
plexes. Assume here that the conductivity of a solution only depends on the number of ions present per unit
volume or on concentration of the ions( which actually is not the case, we will study later that it also depends
on the nature of the on), try and arrange the solution of the following complexes in increasing order of
conductivity.
Secondary valency
S.No. Werner complex Modern notation Ionisation Primary valency satisfied by
satisfied by
3+
1 CoCl3.6NH3 [Co(NH3)6]Cl3 [Co(NH3)6] +3Cl
six (NH3)
three (Cl )
2 CoCl3.5NH3 [Co(NH3)5Cl]Cl2 2+ three (Cl ) including one (Cl )
[Co(NH3)5Cl] +2Cl five (NH3) and one (Cl )
with dual nature
+ three (Cl ) including
3 CoCl3.4NH3 [Co(NH3)4Cl2]Cl [Co(NH3)4Cl2] + Cl
four (NH3) and two (Cl )
two (Cl ) with dual nature
4 CoCl3.3NH3 [Co(NH3)3Cl3] [Co(NH3)3Cl3] three (NH3) and three (Cl )
three (Cl ) all with dual nature
From the above table it is clear that (i) the solution conductivity of complexes 1,2 and 3 corresponds to 1:3,
1:2 and 1:1 electrolyte respectively and thus the increasing order of the conductivity can be represented as
CoCl33NH3 < CoCl3. 4NH3 < CoCl3.5NH3 < CoCl3.6NH3 and (ii) the complexes 1,2 and 3 will react with silver
nitrate and give 3, 2 and 1 mole of the white precipitate of silver chloride.
Ex. For the compound represented by the formula CoCl3.5H2O write down the different complexes possible and
repesent them as per Werners notation and also write down their names.
Sol. CN = 6 octahedral
[CoCl(H2O)5]Cl2; [CoCl2(H2O)4]Cl.H2O; [CoCl3(H2O)3].2H2O;
generally water of crystallization is found with complexes which have bogth cationic and anionic parts, it is
less common with species which are neutral.
Ex. Match the pairs of complexes listed in column-I with the method(s) used for their differentiation
listed in column-II.
Column I ColumnII
(A) [Cr(H2O)6]Cl3 and Cr(H2O)5Cl] Cl2.H2O (p) Can be differentiated by amount, nature or
colour of precipitate formed.
(B) [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br (q) Can be differentiated by electrical
conduction measurement method
(appreciable difference)
(C) [Co(NH3)5Cl]Cl2 and [Co(NH3)6]Cl3 (r) Can be differentiated using cryoscopic
measurement method.
(D) [Cu(H2O)4]SO4.H2O and [Cu(H2O)6](NO3)2 (s) Can be differentiated by heating with
concentrated H2SO4
Ans. (A) p,q,r,s ; (B) p,q ; (C) p,q,r ; (D) p,r,s
Sol. (A) [Cr(H2O)6]Cl3 (aq) [Cr(H2O)6]3+ (aq) + 3Cl (aq)
[Cr(H2O)5Cl] Cl2.H2O (aq) [Cr(H2O)5Cl]2+ (aq) + 2Cl (aq)
(b) [Fe2+(CN)6]4
Number of electrons in Fe2+ = 26 2 = 24
6CN = 6 2 = 12
So, EAN = 24 + 12 = 36 (krypton)
(c) [Fe3+(CN)6]3
Number of electrons in Fe3+ = 26 3 = 23
6CN = 6 2 = 12
So, EAN = 23 + 12 = 35
NOTE :
(a) The EAN rule is generally found to be not valid in case of most of the complexes but in case of metal
carbonyls( which is an important class of comlexes, we will be studying later) this rule is found to be valid in
all cases except one or two exceptions, so do remember it for metal carbonyls and do know how to calculate
the EAN for any metal.
(b) NO ligand is found to act as three electron donar, as indicated by the following reactions in which when the
carbonyl compound is heated in atmosphere of excess of NO.
[Fe(CO)5] + 2NO [Fe(CO)2(NO)2] + 3CO
[Cr(CO)6] + 4 NO [Cr(NO)4] + 6 CO
But also remember that NO+ is only two electron donar
The Werner theory and some other initial bonding theories cannot answer basic questions like.
(i) Why only certain elements possess the remarkable property of forming coordination compounds ?
(ii) Why the bonds in coordination compounds have directional properties ?
(iii) Why coordination compounds have characteristic magnetic and optical properties ?
(b) There is also found some kind of back bonding from metals to the ligands to maintain the charge neutrality.
The extent of this back bonding also depends on the nature of the ligand. We will study about this a bit in
metal carbonyls and all other complexes generally neglect this.
bond It is a partial bond between filled orbitals of metal & vacant of ligand.
The ligands which allow back bonding to sufficient extent are also called acid acceptors. For example
CO, CN, NO etc.
(c) The type of hybridisation of metal & shape of complex involved can be decided conveniently if some chracteristics
of the complex like magnetic nature, geometry or whether exhibits isomerism or not etc. be known. Hence
along with the coordination number some other property must also be given to analyse the com-
plex using VBT.
sp3, dsp2, dsp3 and d2sp3 yield tetrahedral, square planar, trigonal-bipyramidal or square-pyramidal and octa-
hedral spatial arrangements commonly encountered in coordination compounds.
It is found that [Ni(CN)4]2, is diamagnetic in nature. But we know that Ni2+ is paramagnetic with two
unpaired electrons, hence to be diamagnetic the electrons must have got paired up and one d orbital will be
available for the dsp2 hybridisation. For one d-orbital lobe available for hybridisation, pairing of electrons takes
place in the remaining d-orbitals, as shown below in the case of [Ni(CN)4]2,
3d 4s 4p
Ni
Ni2+
[Ni(CN)4]2
CN CN CN CN
dsp2 hybrids used
[Ni(CN)4]2 is square planar and diamagnetic. [NiCl4]2, on the other hand, is paramagnetic and has tetrahe-
dral geometry. In this case, the VB treatment assumes that (i) the d-orbital occupancy remains the same as
in the free Ni2+ ion and (ii) the metal uses sp3 hybrids (involving 4s and 4p orbitals) for bonding with the ligands
as shown below :
[NiCl4]2 is paramagnetic as there are two unpaired electrons.
3d 4s 4p
Ni
Ni2+
[Ni(CN)4]2
Cl Cl Cl Cl
3
sp hybrids used
The VB theory explains the formation of 6 coordinate, octahdral coordination entities by invoking the use of
(n-1)d2nsnp3 or nsnp3nd2 hybrid orbitals by the central metal ion in forming bonds with the ligands. Whether
the hybridisation is dsp3 or sp3d, it can be decided if number of unpaired e or magnetic moment is known to
us else not. An example involving use of (n-1)d2nsnp3 hybrids is the coordination entity, [Fe(CN)6]4, which is
founf to be diamagnetic
The double occupancy of (n-1)d orbitals orbitals confers extra stability and the absence of unpaired electrons
renders this entity diamagnetic.
Ex. Predict the number of unpaired electrons in the square planar [Pt(CN)4]2 ion.
Sol. Pt2+ is a 5d8 ion. For square-planar geometry, dsp2 hybrids are required. For the availability of one d orbital,
pairing of electrons takes place in the remaining d-orbitals. Hence there are no unpaired electrons in [Pt(CN)4]2
ion.
Ex. For the comlex [Ma2 b2], It is given that it does not show geometrical isomerism. Predict the hybridisation.
Sol. CN = 4
Hence either square planar( dsp2 ) or tetrahedral( sp3 ) but since no geometrical isomerism, hence must be
tetrahedral( sp3 ).
CN = 3 The most important geometries for the complexes with CN = 3 are trigonal planar and the trigonal pyramidal.
Examples are the planar HgI3 and [Cu(CN)3]2 and the pyramidal SnCl3.
Ex. [Hg2+33]1
C.N. = 4 This is one of the most important coordination number and results in tetrahedral and square planar geom-
etry.
Ex. Ni (CO)4 (liquid), is found to be diamagnetic, explain the shape and hybridisation.
Sol.
Ex. [NiCl4]2, is found to be paramagnetic with two unpaired electrons, explain the shape and the hybridisation.
CN are strong field ligands (will study in CFT) and therefore they will force the 3d8 electrons to pair up in 4
orbitals.
CN = 5 Coordination number five is less common than coordination number four or six, the possible geometries are
trigonal bipyramidal and the square pyramidal. In most of the complexes these geometries are also found to
interchange into each other. For both these geometries sp3d and dsp3 are two possible hybridisations.
Ex. [Fe(CO)5], this complex is founf to have its total dipole moment to be equal to zero. Explain the hybridisation.
Ex. [Ni(CN)5]3 is found to be dimagnetic with 2 types of Ni C bond lengths out of which four bond lengths are
found to be equal and the fifth one is different. Explain the hybridisation, shape and thus the observed
properties.
Sol. CN = 5
Ex. [Fe(CN)6]4 complex is found to be diamagnetic while the [Fe(CN)6]3 complex is found to be paramagnetic
with one unpaired electron. Explain the shape and hybridisations of both.
Sol. [Fe(CN)6]4
[Fe3+(CN)6]3
Ex. [FeF6]3 complex is found to be highly paramagnetic with five unpaired electrons, explain the shape and
hybridisation.
Sol. Fe3+ 3d5
d ,d
x
2 y 2 z2
or eg
axial d orbitals
For convenience, let us assume that the six ligands are positioned symmetrically along the cartesian axes,
with the metal atom at the origin. As the ligands approach, first there is an increase in the energy of d orbitals
to that of the free ion just as would be the case in a spherical filed. Next, the orbitals lying along the axes (dz2
and dx 2 y 2 ) get repelled more strongly than dxy, dyz and dxz orbitals, which have lobes directed between the
axes. The d xy , d yz , dxz orbitals are lowered in enrgy relative to the average energy in the spherical crystal
filed. Thus, the degenerate set of d orbitals get split into two sets : the lower energy orbitals set, t2g and the
higher enrgy, eg set. The energy seperation is denoted by 0 (the subscript o is for octahedral (Fig.)
General formula : CFSE = [ 0.4 (n) t2g + 0.6 (n) eg] o + nP.
where n & n are number of electron(s) in t2g & eg orbitals respectively and o crystal field splitting energy for
octahedral complex. n represents the number of extra electron pairs formed because of the ligands in
comparison to normal degenerate configuration.
On the basis of the behaviour (the splitting produced with different metal ions) of ligands these are arranged
in a series according to their strentgh which is called Spectrochemical Series.
weak Ligand
I<Br < S2 < SCN < Cl < NO3 < N3 < F < OH < C2O24 < H2O <
NCS < CH3CN < Py < NH3 < en < bpy < NO 2 < PPh3 < CN < CO
Strong Ligand
Do note one thing in the series that in all strong field ligands the donor atom is either Nitrogen atom or
Carbon atom while in all weak field ligands the donar atoms are either Oxygen atoms or Sulphur or halogen
atoms.( Remember)
The intermediate ligands can in some cases act as strong field ligands or can also act as weak field ligands
depending on the nature of the metal involved or some other factors. Generally for kexamples in our
course we can consider ligands upto water as weak and beyond water as strong. But do remember
the following exception.
Ex. [Co(C2O4)3]
Co3- 3d6 t2g2, 1, 1 eg 1,1
If C2O24 is considered W.L. sp3d2 and paramagnetic with four unpaired electrons.
high spin /outer orbital complex.
If C2O24 is considered S.L d2sp3 and diamagnetic
t2g2,2,2 eg 0,0 low spin/inner orbital complex.
Ex. What is electronic configuration of Fe2+ in complex [Fe(CN)6]4 and in complex [FeF6]3
Sol. [Fe(CN)6]4 Fe+2 3d6 t2g2,2,2 eg0,0 d2sp3
Ex. In the complex [Fe(Cl)(CN)4(O2)]4 , the electronic configuration of metal ion in this ligand field is found to be
t2g2,2,2, eg0,0. Then find out whether the complex is paramagnetic or diamagnetic and whether the OO bond
lentgh in the complex is more than that in dioxygen O2. Also write the IUPAC name of the complex.
Sol. 3d6 Fe2+ O21 superoxido
Bond order = 1.5
Diamagnetic Paramagnetic (1)
B.L. more than O2
Chlorotetracyano superoxidoferrate (II) ion.
In tetrahedral complexes none of the ligand is directly facing any orbital so the splitting is found to be small
in comparison to octahedral complexes. For the same metal, the same ligands and metal-ligand distances,
it can be shown that t = (4/9)o. This may attributes to the following two reasons.
(i) there are only four ligands instead of six, so the ligand field is only two thirds the size ; as the
ligand field spliting is also the two thirds the size and (ii) the direction of the orbitals does not
concide with the direction of the ligands. This reduces the crystal field spliting by roughly further
2 2 4
two third. So t = = o.
3 3 9
Consequently, the orbital splitting energies are not sufficiently large for forcing pairing and, there-
fore, low spin configurations are rarely observed.
2
2
Ex. Ni Cl4 calculate the CFSE of this tetrahedral complex.
Sol. Ni2+ 3d8 4s0p0
Weak filed ligand
Configuration of Ni(II) in tetrahedral field P = eg2, 2, t2g 2,1,1
t P(2)
For square planar geometry one d-orbital must be vacant.
So hybridisation sp3
3 2
CFSE = 4 t + 4 t = 2.4 t + 1.6 t = 0.8 t.
5 5
In tetrahedral complexe, all ligands are considered to be weaker ligands and, therefore, electrons filling takes
place continuously from equal to t2g.
[MnO4] d3s / sp3
permanate tetrahedral
ion
Examples :
2 2
2 2
3d10 , [ Z n(NH3 )4 ] ; 3d10 , [ Zn(CN)4 ] CFSE = O (diamagnetics)
[Ni(CO)4] diamagnetics
[NiCl4]2 paramagnetics with two unpaired electrons.
[NiCl2 (pph3)2] paramagnetics with two unpaired electrons.
[MnCl4]2 paramagnetics with five unpaired electrons.
[FeCl4]2 paramagnetics with four unpaired electrons.
[Cu(py)4]+ diamagnetics.
Cs2 [CuCl4] orange tetrahedral paramagnetics with one unpaired electrons.
(NH4)2 [CuCl4] yellow square planaer paramagnetics with one unpaired electrons.
But, sp = (1 + 2 + 3) > o
and sp = 1.3 o.
Important factors which determine the magnitude of the orbital splitting energy, are :
(i) Oxidation state of the metal ion : Generally, the higher the ionic charge on the central metal ion, the
greater the value of .
(ii) Nature of the metal ion : For analogous entities within a group, the values differ. The general trend
being 3d < 4d < 5d. Thus while going from Cr to Mo or Co to Rh, the 0 value increases by ~ 50%. As a
consequence of this, coordination entities have a greater tendency to be low spin as compared to the first
transition series.
(iii) Geometry of the coordination entity : The t value is only ~ 50% as large as that of 0.
sp > 0 > t
approximately, for the same set of ligands
sp 1.3 0
4
t
9 0
(iv) Nature of the ligand : The ligands can be arranged in the order of increasing field strength.
With strong field ligands, increases
With weak field ligand, decreases.
Relationship between the wavelength of light absorbed and the colour observed In some
coordination entitles
You need not remember the above table, you will be provided with it whenever the question is asked and also
you need not remember the color of the complexes except some common complexes which will be used in
qualitative analysis and hence in detection of different ions.
Note : (a) In absence of ligand, crystal field splitting does not occur and as a consequence the substance
appears colourless. For example (i) removal of water from violet coloured complex [Ti(H2O)6]Cl3 on heating
makes it colourless. (ii) Similarly anhydrous copper sulphate (CuSO4) is white, but hydrated copper sulphate
(CuSO4.5H2O) is blue coloured.
(b) The nature of the ligand and the molar ratio of metal : ligand also influence the colour of the complex for
example in the pale green complex of [Ni(H2O)6], the colour change is absorbed when ethylenediamine is
progressively added to it.
Note : Ruby is Al2O3 in which 0.51% Cr3+ ions (d3 electron system) are randomly distributed in the positions
normally occupied by Al3+. We may consider Cr(III) species as octahedral Cr(III) complexes incorporated into
n, the stability constant, is related to thermodynamic stability when the system has reached equilibrium.
Most of the measurements have been made from aqueous solutions, which implies that the complex is
formed by the ligand displacing water from the aqua complex of the metal ion. Ignoring the charge and taking
L as un unidentate ligand, the stepwise formation of the complex is represented as shown above. K1, K2, K3
..... Kn representing the stepwise stability (or formation) constants.
The above is thermodynamic stability criteria, there can be another kind of stability called Kinetic Stability,
which measures the rate of ligand replacement.
The value of stability constant for some of the complexes are given below:
Complex Stability constant
[Cu(NH3)4]2+ 4.5 1011
[Ag(NH3)2]2+ 1.6 107
[Co(NH3)6]2+ 1.12 1011
[Co(NH3)6]2+ 5.0 1033
[AgCl2] 1.11 105
[AgBr2] 1.28 107
[Ag(CN)2] 1.0 1022
[Cu(CN)4]2 2.0 1027
[Fe(CN)6]3 7.69 1043
The above table is only for teachers information, we dont expect the students to remember the constants or
the order of stability of the complexes.
Important generalizations derived from the vast data on stability constants are :
For a given metal and ligand the stability is generally greater, the greater the charge on the metal
ion. Thus, stability of coordination entities of ions of charge 3+ is greater than the entities of 2+ ions. Further,
for the divalent ions of the first row transition elements, irrespective of the ligand involved, the
stabilities vary in the Irving-Williams order :
MnII < FeII < CoII < NiII < CuII > ZnII
This order is according to the size of the ions, smaller the size of the ion or greater the charge density on the
metal greater is the stability of the complex.
The stability also depends on the formation of chelate rings. If L is an unidentate ligand and LL, a
didentate ligand and if the donor atoms of L and LL are the same element, then LL will replace
L. The stabilisation due to chelation is called the chelate effect. It is of great importance in biological
systems and analystical chemistry. The chelate effect is maximum for the 5- and 6-membered rings. In
general, rings provide greater stability to the complex.
If a multidentate ligand happens to be cyclic and there are no unfavourable steric effects, a further increase
in stability occurs. This is termed the macrocyclic effect.
A special form of ionisation isomerism is the so called Hydrate isomerism. It occurs when water forms a
part of the coordination entity or is outside it. For example, CrCl3 . 6H2O exists in three distinct isomeric
forms : [Cr(H2O)6]Cl3, violet ; [CrCl(H2O)5]Cl2.H2O, pale green : [CrCl2(H2O)4]Cl.2H2O, dark green. Apart from
their distinctive colours, the three isomers can be identified by the addition of excess of aqueous silver nitrate
to their aqueous solutions, which precipitates chloride in the molar ratio of 3 : 2 : 1 respectively.
Complex Reaction with AgNO3 Reaction with conc. H2SO4(dehydrating agent)
[Cr(H2O)6]Cl3 in the molar ratio of 3:1 No water molecule is lost or no reaction
[CrCl(H2O)5]Cl2.H2O in the molar ratio of 2:1 one mole of water is lost per mole of complex
[CrCl2(H2O)4]Cl.2H2O in the molar ratio of 1:1 two mole of water is lost per mole of complex
Ma2 b2 M M
a b b a
Cis trans
Ma2bc M M
a c b a
Cis trans
Mabcd 3 (ab)(cd) aTb
(ac)(bd) aTc
(ad)(bc) aTd
a b a d
Mabcd M M
d c c b
aTc aTb
a b
c d
aTd
M(AA)a2 0 (Aa)(Aa)
M(AA)ab 0 (Aa)((Ab)
M(AB)a2 0 (Aa)(Ba)
M(AB)ab 2 (Aa)(Bb)
(Ab)(Ba)
A a A b
M M
B b B a
M(AA)2 0 (AA)(AA)
M(AB)2 2 (AB)(AB)
(AA)(BB)
A A A B
M(AB)(AB) M M
B B B A
M(AA)(BB) 0 (AB)(AB)
M(AA)(CD) 0 (AC)(AD)
M(AB)(CD) 2 (AC)(BD)
(AD)(BC)
A C A D
M(AB)(CD) M M
B D B C
ATD ATC
i Ma6
no.G.I only one form is possible ( both will be optically inactive)
ii Ma5b
(iii) Ma2b4 2 (aa)(bb)(bb) (optically inactive)
(ab)(ab)(bb) (optically inactive)
b b a
b a b a b b
Ma2b4 M M
|||
M
b a a b b b
b b a
a c b
a b a b a a
M M
|||
Ma4bc M
a c a a a a
a a c
Cis Trans
b b
a b a b
Ma3b3 M M
a a a
b
a b
b b
a b b a
M M
a b a a
a b
Fac- (a) Mer-
NH3 NH3
O2N NH3 H2N NO2
Co Co
NO2 NO2
Fac- Mer-
(b)
(vi) Ma3b2c 3
The trans pairs for the three isomers are
(aa)(ab)(bc) (optically inactive)
(aa)(bb)(ac) (optically inactive)
(ab)(ab)(ac) (optically inactive)
(vii) Ma3bcd 4
The trans pais for the four possible isomers are
(aa)(ab)(cd) (optically inactive)
(aa)(ac)(bd) (optically inactive)
(aa)(ad)(bc) (optically inactive)
(ab)(ac)(ad) (optically active)
(viii) Ma2b2c2 5
The trans pairs for the possible isomers are
(aa)(bb)(cc) (optically inactive)
(aa)(bc)(bc) (optically inactive)
(bb)(ac)(ac) (optically inactive)
(cc)(ab)(ab) (optically inactive)
(ab)(ac)(bc) (optically active)
(x) Ma2bcde 9
(xi) Mabcdef 15
a
a A
a A
b a
A a A a
M(AA)a3b 2 M M
A a A b
b a
bTa aTa
a a b
A b A a A
M(AA)a2b2 3
M M M
A b A b A
a b b
M(AA)abcd 6
M(AA)3 1 form (No G.I.)
MI(AB)3 2 form
A A
A A A B
Fac. M Mer. M
B B B B
B B
[Pt(py)NH3NO2ClBrI]
py py
py NO2 O2 N py
Pt Pt
Cl NH3 H3N Cl
I I
d-isomer Mirror l-isomer
3+ 3+
en en
en
Co Co
en
en en
d-form Mirror l-form
N en + en N +
H3N N N NH3
Cr Cr
H3N Cl Cl NH3
Cl Cl
METAL CARBONYLS :
A widely studied and important class of organometallic compounds is that of metal carbonyls. Binary com-
pounds of metals with CO are called metal carbonyls. The homoleptic carbonyls (compounds containing
carbonyl ligands only) are formed by most of the transition (d metals). The metals constituting the central
part of the d block form stable, neutral binary
carbonyls like : [V(CO)6], [Cr(CO6], [Mo(CO)6],
[W(CO6], [Mn2(CO)10], [Fe(CO)5], [Fe2(CO)9],
[Co2(CO)8], [Co4(CO)12], [Ni(CO4)], etc. Outside
the central part of d-block, the metal carbonyls
are usually unstable.
The MO energy level diagram for CO The filled 3 and the vacant 2 oribttols are important
for bonding in the formation of metal carbonyls.
M C O
(i) As M C bonding increases, the C O bond becomes weaken. The greater the positive charge on the
central metal atom, the less readily the metal can donate electron density into the * orbitals of the carbon
monoxide ligands to weaken the C O bond.
(ii) In contrast, in the anionic complex (i.e. carbonylate anion) the metal has a greater electron density to be
dispersed, with the result that M C bonding is enhanced and the C O bond is diminished in strength.
For example in isoelectronic complexes the strength of metal-ligand bond increases and strength of C O
bond in CO decreases (because bond order decreases) as the negative charge on the complexes increases.
Thus order of CO bond strengths ;
(a) [M(CO)6]+ > [Cr(CO)6] > [V(CO)6] > [Ti(CO)6]2.
(b) [Ni(CO)4] > [Co(CO)4] > [Fe(CO)4]2.
Classification of metal carbonyls
Ni(CO) 4
Fe(CO)5 Fe 3 (CO)12
3d
Cr(CO)6 Mn2CO10 CO 4 (CO)12
V(CO)6
Mo(CO)6
4d
Ru(CO)5
W (CO)5
5d
Os(CO)6
Note : Besides the metal carbonyls, there are some metal carbonyl anions which generally form salts with alkali
metal ions.
Ex : Na[V (CO)6]1 Sodium hexacarbonyl vanadate (I)
K2[Ni2(CO)6]
Octahedral
H H
C
||
Cl C
K [PtCl3 (2 C2H4 )] K+
Pt H H
Cl Cl