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Studies on schiff base transition metal complexes derived from benzil, p-

nitroaniline and 2, 2'-bipyridyl

Article · January 2015

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Journal of Chemical and Pharmaceutical Research, 2015, 7(10S):111-119

ISSN : 0975-7384
Research Article CODEN(USA) : JCPRC5

Studies on schiff base transition metal complexes derived from benzil,

p-nitroaniline and 2, 2’-bipyridyl
A. Kulandaisamy* and A. Palanimurugan

Department of Chemistry, Raja Doraisingam Government Arts College, Sivagangai, Tamilnadu, India
_____________________________________________________________________________________________

ABSTRACT

A new series of biologically active transition metal complexes of Cu(II), Ni(II), Co(II), Zn(II) and VO(IV) ion have
been synthesized from the benzilidene-p-nitroaniline and 2,2’-bipyridyl. The structural features of the synthesized
complexes have been arrived from their elemental analyses, FAB-mass, IR, UV-Vis., 1H-NMR and ESR spectral
studies. From the observed data, all the complexes are square -planar geometry except vanadyl complex which
shows square pyramidal geometry. Monomeric and electrolytic natures of the complexes were confirmed for their
magnetic susceptibility and molar conductivity measurements. Cyclic voltammogram of copper complex was
recorded in MeCN solution at 300 K and their salient features well reported. Antimicrobial screening tests gave
good results in the presence of metal ion in the ligand system.

Keywords: Schiff base, benzil, p-nitroaniline, Bipyridyl, Electronic spectra, ESR spectra
_____________________________________________________________________________________________

INTRODUCTION

The coordinating property of benzil has been modified into flexible ligand system by condensation with a variety of
primary amines which have some additional functional groups like phenolic hydroxyl, thiol, nitrogen atom, etc.
Benzil acts as a diketones like acetylacetone, acetoacetanilide etc. are continued to attract considerable attention
from both theoretical points concerning the mode of bonding and their general reactivity as coordinated ligands. The
azomethine group of Schiff’s base plays an important role for showing excellent biological activities [1]. Some
Schiff bases were tested for fungicidal activity, which is related to their chemical structure [2]. A considerable
number of articles have been published on the spectral behavior of Schiff bases and their application in different
fields [3–8]. Furthermore, aniline derivatives condensed with benzil, the resulting product acts as a bidentate ligand
system towards the biologically important metal ions. According to the literature survey, it may be concluded that
there is a great diversity to synthesize novel transition metal complexes based on the choice of ligands. In view of its
medicinal use much concern is focused on Schiff base ligands due to the presence of donor atoms. So there is broad
scope for undertaking a well-organized study of coordination complexes of transition metals with variety of Schiff’s
base ligands [12-15]. Hence, in this paper, we report the synthesis, spectral, redox and antimicrobial activities of
mixed ligand complexes derived from benzilidene-p-nitroaniline and 2,2’-bipyridyl.

EXPERIMENTAL SECTION

2.1. Materials and measurements

All of the chemicals and reagents used in the synthesis were purchased from Fluka and Merck Chemical companies
and were used without further purification. Spectroscopic grade solvents were used for spectral and cyclic
voltammetric measurements. FAB mass spectra were recorded on a JEOL SX 102/DA-6000 mass spectrometer,
using m-nitrobenzyl alcohol as a matrix, at Indian Institute of Chemical Technology, Hyderabad. Elemental analyses
(C, H, N) were carried out with Thermofinger –Flash CA 1112 series at Sophisticated Analytical Instrumentation
facility, Indian Institute of Technology, Mumbai. The molar conductance of the complexes in 10-3 M MeCN solution

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A. Kulandaisamy and A. Palanimurugan J. Chem. Pharm. Res., 2015, 7(10S):111-119
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was measured using a 305 type systronic conductivity bridge with a dip type cell. H1-NMR spectra of the Schiff
bases and their zinc complexes were recorded in CDCl3 solution on a Brucker 300 MHz FT-NMR spectrometer
using TMS as internal standard at Madurai Kamaraj University, Madurai. The UV-Visible spectra of the compounds
were recorded on a systronics UV-Vis., spectrophotometer. The IR spectra were recorded on a FT-IR 8400S
Shimadzu spectrophotometer in the 4000 – 400 cm-1 range using KBr as solvents. Cyclic voltammogram of the
copper complexes was recorded in MeCN solution at 300 K using a BAS CV50 electrochemical analyzer. The three
electrode cell contains a reference Ag/AgCl electrode, Pt wire auxiliary electrode and glassy carbon working
electrode. Tetra butyl ammonium bromide (TBAB) was used as supporting electrolyte. The X-band ESR spectra of
the copper complexes in MeCN solution at 300 K and 77 K were recorded on a Varian E-112 ESR spectrometer
using DPPH as the g – marker at Sophisticated Analytical Instrumentation facility, IIT, Mumbai.

2.2. Synthesis of Schiff base (L)

An ethanolic solution 20 mL of 1:2 of benzil (2.03 g, 10 mmol) and p-nitroaniline (2.76 g, 20 mmol) mixture was
refluxed for ca 6 h in the presence of anhydrous potassium carbonate. It was filtered and and cooled. The solid
product obtained was separated by filtration. The product was recrystalised from ethanol. Yield: 60% (m.p. 86°C).
The scheme for the synthesis of Schiff base is given below:
Ph Ph
NH 2

Ph K2CO3
Ph Ethanol N N
+ 2 + 2H2O
Reflux 6 h
O O Filter
Benzil Cool
NO2
p-nitroaniline
NO2 NO2
2.3. Synthesis of mixed – ligand complexes: The scheme for the synthesis of mixed ligand complexes are given
below:
Ph Ph

N N N N
+ + MCl2
Metal salt
2,2'-Bypyridyl

Ethanol
NO2 NO2 Reflux 12 h
Schiff base Cooled

2+
Ph Ph

O2N N N NO2
M
2Cl
N N

Where, M= Cu(II), Ni(II), Co(II), VO(II) and Zn(II)

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A. Kulandaisamy and A. Palanimurugan J. Chem. Pharm. Res., 2015, 7(10S):111-119
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An ethanolic (20 ml) solution of Schiff base L (10 mmol) and metal(II) chloride (10 mmol) was refluxed for 2 h on a
water bath. Add (10 mmol) ethanolic solution of 2,2’-bipyridyl and then refluxed the mixture for ca. 12 h. The
resulting solution was concentrated and cooled at 0°C. The precipitated complexes were filtered, washed with
ethanol and dried in vacuo.

RESULTS AND DISCUSSION

The analytical data along with some physical properties of the complexes are summarised in Table 1. The ligands,
on interaction with Cu(II), Co(II), Ni(II), Zn(II) and VO(II), yields complexes corresponding to the general formula
[MC36H26N4O2]Cl2. They are soluble in common organic solvents. The high molar conductance values of the
complexes reveal their electrolytic nature[12]. The magnetic susceptibility data of the complexes in the solid state
shows that Cu(II), Co(II) and VO(II) are paramagnetic, Ni (II) and Zn(II) are diamagnetic at room temperature.
Table 1. Physical characterizations and analytical data of the complexes

Found (Calcd.) (%) ΛM x 10-2 µeff. (BM)

Compound Colour M C H N Cl (mho cm2 mol-1)
L Reddish-brown - 78.64 (80.00) 4.76 (4.62) 7.63 (7.18) - - -
[CuL(bipy)]Cl2 Brown 9.04 (9.34) 63.09 (63.48) 3.94 (3.82) 8.33 (8.23) 10.68 (10.43) 86.3 1.76
[NiL(bipy)]Cl2 Brown 8.64 (8.69) 63.12 (63.93) 3.65 (3.85) 8.14 (8.29) 10.89 (10.51) 74.6 -
[CoL(bipy)]Cl2] Green 8.46 (8.72) 63.32 (63.91) 3.48 (3.85) 8.62 (8.28) 10.84 (10.50) 78.5 3.91
[ZnL(bipy)]Cl2 brown 9.84 (9.62) 63.79 (63.28) 3.62 (3.81) 8.42 (8.20) 10.46 (10.40) 86.2 -
[VO(bipy)]Cl2 Green 7.78 (7.45) 63.28 (63.16) 3.24 (3.80) 8.12 (8.19) 9.94 (10.38) 64.7 1.86

The FAB mass spectral data (m/z values) of the Schiff base and its copper complexes were compared with their
molecular formula weight. The mass spectra of Schiff base and its copper complex shows a molecular ion peak at
390 and 681 respectively. These data are in good agreement with the proposed molecular formula for these
complexes i.e., [MC36H26N4O2]Cl2, where M= Cu(II), Ni(II), Co(II), VO(II) and Zn(II). In addition to molecular ion
peak, the spectra exhibited peaks assignable to various fragments arising from the thermal cleavage of the ligand and
its complex.

The IR spectrum of the ligand shows the characteristic -C=N bands in the region 1630-1600 cm-1, which are also
shifted to lower frequencies in the spectra of the complexes (1600-1560 cm-1). IR spectra of free Schiff base shows
its characteristic bipyridyl ring vibration at 1045 and 660 cm-1 region which are shifted to lower frequencies in all
the spectra of the complexes (1030 and 635 cm-1 region), confirming the presence of coordinated bipyridyl group
[17, 18]. The IR spectra of the metal chelates also show some new bands in the region 480-450 cm-1 and 400-350
cm-1 which are probably due to the formation of M-O and M-N bonds respectively [19]. In addition to the other
bands, the vanadyl complex show an additional band at 930 cm-1 attributed to the V=O frequency. The ligand and
the complex exhibits their characteristic –C-H aromatic group absorption bands in the 3111-3108cm-1 region. The
IR data of some important peaks of the ligand and all the complexes are summarized in Table 2.

Table 2 IR spectral data of the Schiff base and its mixed ligand complexes (cm-1)

Compound ν(C-H) ν (C=N) ν(C–N) ring ν(M–O) ν(M–N)

L 3107 1597 1298 - -
[CuL(bipy)]Cl2 3110 1573 1210 515 451
[NiL(bipy)]Cl2 3108 1584 1242 508 456
[CoL(bipy)]Cl2] 3108 1580 1242 508 454
[ZnL(bipy)]Cl2 3109 1589 1242 512 452
[VO(bipy)]Cl2 3111 1575 1248 592 453

The 1H-NMR spectrum of the Schiff base and its zinc complex are shown in Figure 1. The 1H-NMR spectrum of the
Schiff base exhibits a multiplet signal at 7.3–7.8 d (m, Ar-H). This signal in the spectrum of the zinc complex is
shifted downfield compared to the free ligand, suggesting deshielding of the azomethine group due to the
coordination with metal ion. The zinc complex also exhibits some new peaks around 2.9 – 3.5 ppm (multiplets) and
6.9-7.2 ppm (multiplets) indicates that the existence of bipyridyl group in the complexes.

The UV-Vis. spectrum of copper in MeCN shows two d-d bands which are assigned as 2B1g → 2B2g (532 nm) and
2
B1g → 2A1g (802 nm) transitions. The d-d transition at 532 nm strongly favors square planar geometry around the
metal ion[20]. The nickel complex in MeCN shows a d-d band at 676nm, assigned as 1A1g → 1B1g transition which
indicates square planar geometry[21]. The cobalt complex in MeCN shows a d-d band at 646 nm, assigned as 1A1g
→ 1B1g transition which confirms the square planar geometry [22,23]. The vanadyl complex in MeCN solution
shows three d-d bands at473 nm, 619 nm and 828 nm which are assigned as 1B2 → 2A1, 1B2 → 2B1 and 1B2 → 2E

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A. Kulandaisamy and A. Palanimurugan J. Chem. Pharm. Res., 2015, 7(10S):111-119
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respectively. Square pyramidal geometry is proposed for this system [23] because it shows a band in the 828 nm
region (1B2 → 2E). This is further confirmed by the ESR spectral data.

Figure 1 1H NMR Spectra of the Schiff base and its mixed ligand zinc complex (b) in CDCl3 Solution

The absorption regions, assignments and the proposed geometry of the complexes are given in Table 3.
Table 3 Electronic absorption spectral data of the compounds

Compound Solvent Absorption region (nm) Band assignment Geometry

(L) MeCN 302 INCT
338 INCT -

[CuL(bipy)]Cl2 MeCN 315 INCT

344 INCT
532 2
B 2g → 2B 1g
Square-planar
802 2
B2g → 2A1g

[NiL(bipy]Cl2 MeCN 304 INCT

329 INCT
1
676 A1g→1B1g Square-planar

[CoL(bipy]Cl2 MeCN 316 INCT

332 INCT
1
646 A1g→1B1g Square-planar

[VOL(bipy]Cl2 MeCN 323 INCT

352 INCT
473 2
B2 → 2A1
619 2
B2 → 2B1
Square-pyramidal
828 2
B 2 → 2E
INCT = Intraligand charge transfer band

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A. Kulandaisamy and A. Palanimurugan J. Chem. Pharm. Res., 2015, 7(10S):111-119
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The cyclic voltammogram of the copper complex in MeCN solution (Figure 2) shows a quasi-reversible peak for the
couple: Cu(II) → Cu(III) at Epa = 0.61 V with the direct cathodic peak for Cu(III) → Cu(II) at Epc = 0.38 V. Further,
it exhibits another couple in the negative region characteristic for Cu(II) → Cu(I) (Epc = - 0.5 8 V) reduction and
Cu(I) → Cu(II) (Epa = - 0.18 V) oxidation. The single - electron transfer nature of the two couples is established by
the comparison of Ipc and Ipa values [24].

Current (µA)

E(V) Ag/AgCl

Figure 2. Cyclic voltammogram of the [CuL(bipy)]Cl2 complexes in acetonilrile (0.1M TBAP). Scan rate 100 mVs-1

The X-band ESR spectra of copper complex in DMSO solution at 300 and 77 K are shown in Figure 3.

The spectrum of the copper complex at 300 K shows one intense band in the high field region, which are isotropic
due to tumbling motion of the molecules. The splitting of intense peak at 300 K may be due to internal standard
(DPPH). However this complex at 77 K shows well-resolved peaks with low intensities in the parallel region and
one intense peak in perpendicular region. The absence of a half field signal at 1600 G corresponding to the ∆Ms =
±2 transition, rules out any Cu-Cu interaction in the ESR spectrum[25]. The ESR parameters gll, g⊥, All and A⊥ were
determined from the anisotropic spectra of the frozen solutions (magnetically diluted solids). The g tensor values of
the copper complexes can be used to derive the ground state. In square planar complexes, the unpaired electron lies
in the dx2_y2 orbital giving 2B1g as the ground state with gll > g⊥> 2, while the unpaired electron lies in the dz2 orbital
giving 2A1g as the ground state with g⊥ > gll > 2. From the observed values, it is clear that All (150 x 10-4 cm-1) > A⊥
(77 x 10-4 cm-1) and gll (2.32) > g⊥ (2.08) > 2 and the parameters of the complex coincide well with related systems
which suggest that the complex has square planar geometry and the system is axially symmetric [26,27]. The ESR
parameters and the d-d transition energies were used to evaluate the bonding parameters α2, β2 and γ2 for the Cu(II)
ion in various ligand field environments which may be regarded as measures of the covalence of the in-plane σ-
bonds (α2), in-plane π-bonds (β2) and out-of-plane π-bonds (γ2) respectively32. The observed value of α2 (0.86)
indicates that complex have some covalent character. The observed β2 (1.04) and γ2 (1.02) values indicate that there
is no substantial interaction in the out-of-plane π-bonding and in-plane π-bonding which are completely ionic.

The ESR spectra of the vanadyl complex were recorded in DMSO solution at 300 and 77 K and are shown in Figure
4. The room temperature (300 K) spectrum is a typical eight line pattern which shows that single vanadium is
present in the molecule, i.e. it is a monomer. In the frozen solid state, the spectrum shows two types of resonance
component: one set due to the parallel features and the other set due to the perpendicular features which show an
axially symmetric anisotropy with well resolved sixteen-line hyperfine splitting characteristic of an interaction
between the electron and the vanadium nuclear spin.

The various parameters calculated from the spectrum of the complex [A║ (193 x 10-4 cm-1) > A⊥ (86 x 10-4 cm-1)
and g⊥ (2.02) g⊥ (1.90)] indicate that the complex is square pyramidal geometry, characteristic for the oxovanadium
(IV) chelates. The bonding parameters of this complex can be calculated with the help of optical spectra of the
complex [28,29].

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A. Kulandaisamy and A. Palanimurugan J. Chem. Pharm. Res., 2015, 7(10S):111-119
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The in-plane π-bonding β2 (1.02) and out-of-plane π-bonding coefficients γ2 (0.98) values do not deviate much from
unity. This is consistent with Kivelson’s conclusion, which suggests that the dxy orbital is essentially non-bonding
while π-bonding coefficients remain constant. Essentially, the delocalization of electrons into the ligand may be
gauged form the in-plane σ-bonding coefficients (α2) values. This follows the σ-donor strength of the ligand and it
usually decreases as the covalent bonding increases. The observed α2 (0.85) value indicates that the in-plane σ-
bonding is significant. The molecule orbital coefficients also show that the metal ion has some covalent character in
ligand environment.

Figure 3. ESR spectrum of copper complex at 300 K (a) and 77 K (b) in DMSO solution

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A. Kulandaisamy and A. Palanimurugan J. Chem. Pharm. Res., 2015, 7(10S):111-119
______________________________________________________________________________

Figure 4. ESR spectrum of vanadyl complex at 300 K(a) and 77 K (b) in DMSO solution

Biological studies - In vitro antimicrobial activity

The in vitro biological screening effects of the investigated compounds were tested against bacteria: Escherichia coli
Staphylococcus aureus, Salmonella typhi, Bacillus subtilis and Klebsiella pneumonia. The mimimum inhibitory
concentration against the growth of microorganisms is reported in Table 4. It indicates that most of the complexes
have higher toxicity against the organisms. A comparative study of the ligands and their complexes indicates that
most of the metal chelates exhibit higher antibacterial activity than the free ligands.

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A. Kulandaisamy and A. Palanimurugan J. Chem. Pharm. Res., 2015, 7(10S):111-119
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Table 4 Antimicrobial activity results of the Schiff base ligand and its complexes(MIC value in mg/l)

Compound Escherichia coli Salmonella typhi Klebsiella pneumonia Staphylococcus aureus Bacillus subtilis
L 20.2 16.5 15.2 22.5 18.4
[CuL(bipy)]Cl2 14.3 11.2 10.5 9.5 13.2
[NiL(bipy)]Cl2 12.5 12.5 12.2 15.2 16.5
[CoL(bipy)]Cl2] 18.2 16.4 10.2 11.5 13.8
[VOL(bipy)]Cl2 10.8 18.6 12.0 14.2 16.2
[ZnL(bipy)]Cl2 10.5 12.2 10.2 9.5 10.4
Amikacin* 19.2 20.5 20.5 18.5 16.2
* Standard.

The results show that the metal chelates are more activity than their parent ligands against the same microorganism
and under identical experimental conditions. The increase in antifungal activity of the metal chelates may be due to
the effect of the metal ion on the normal cell process. A possible mode for toxicity increase may be considered in the
light of Tweedy’s chelation theory [21. Antimicrobial screening tests gave good results in the presence of metal ion
in the ligand system. The Zn(II) complex shows greater antimicrobial activity than all other compounds because of
its greater lipophilicity.

CONCLUSION

NEW bidentate Schiff base was prepared and it is used for complexation with transition metal ion like Cu(II), Ni(II),
Co(II), Zn(II) and VO(II). All the synthesized compounds were characterized by elemental analysis, molar
conductance, magnetic susceptibility measurement, 1H NMR, IR, FAB mass and ESR spectral data. From the
characterization, all the complexes are square planar geometry except vanadyl complex which shows square
pyramidal geometry. Monomeric and electrolytic natures of the complexes were confirmed for their magnetic
susceptibility and molar conductivity measurements respectively. The cyclic voltammogram of the copper complex
in MeCN solution shows a quasi-reversible peak for the couple: Cu(II) → Cu(III) at Epa = 0.61 V with the direct
cathodic peak for Cu(III) → Cu(II) at Epc = 0.38 V. Further, it exhibits another couple in the negative region
characteristic for Cu(II) → Cu(I) (Epc = - 0.5 8 V) reduction and Cu(I) → Cu(II) (Epa = - 0.18 V) oxidation. The in
vitro biological screening effects of the investigated compounds were tested against bacteria: Escherichia coli
Staphylococcus aureus, Salmonella typhi, Bacillus subtilis and Klebsiella pneumonia.. Antimicrobial screening tests
gave good results in the presence of metal ion in the ligand system. The Zn(II) complex shows greater antimicrobial
activity than all other compounds because of its greater lipophilicity.

Acknowledgements
We are grateful to the authorities of the RDGA College for encouragement. We also thank the Indian Institute of
Technology (IIT), Chennai for the use of their ESR facilities. We record our sincere thanks to Lady doak college,
Madurai (CHN analysis), Dr Muthusubramanian, School of Chemistry, Madurai Kamaraj University, Madurai (1H
NMR facities), Dr J Dhaveethuraja Department of Engineering Chemistry, Mohammed Shathak Engineering
College, Ramnad (IR facilities) and Dr. Nagendran Department of Chemistry, Alagappa Government Arts college,
Karaikudi for UV-Vis spectrometer facilities..

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