Ms Vandana Pandey PHD Thesis

STUDIES ON THE METAL COMPLEXES OF FIRST
AND SECOND TRANSITION SERIES

A
THESIS
SUBMITTED
BY
VANDANA PANDEY
(Regn. No. 2K05-NITK-1075)
FOR THE AWARD OF DEGREE OF
DOCTOR OF PHILOSOPHY
IN
CHEMISTRY
UNDER THE SUPERVISION OF
Dr. DINESH KUMAR
DEPARTMENT OF CHEMISTRY
NATIONAL INSTITUTE OF TECHNOLOGY
KURUKSHETRA-136119
HARYANA, INDIA
2011
CONTENTS
Foreword
i- iv
INTRODUCTION
1-116
Chapter 1
Coordination compounds of Schiff base containing urea

moiety
Chapter 2
1 1 7- 1 2 4
Ligational behavior of the azetidin-2-one derived from

salicylaldehyde and o-hydroxyphenylurea towards some di-,
tri- and hexavalent metal ions
Chapter 3
125-129
Physico-chemical studies on the coordination compounds of

thiazolidin-4-one derived from salicylaldehyde and ohydroxyphenylurea
Chapter 4
130-135
Studies on the coordination compounds of the polystyreneanchored Schiff base obtained from the condensation of
chloromethylated polystyrene, 3-formylsalicylic acid and ohydroxyphenylurea
136-141
Appendi x-1
Abbreviations
142-143
Appendi x-2
Materials and sources
144-145
Appendi x-3
Analyses and physical measurements
146-147
Appendi x-4
Tables at a glance
148-156
Appendix-5
Figures at a glance
157-196
References
1 9 7 - 2 15
Summary
2 1 6 - 2 17
Future scope
2 1 8 - 2 18
List of published papers and their reprints
FOREWORD
The Thesis contains General Introduction, four Chapters dealing with the
syntheses, elemental analyses, spectral studies and the magnetic susceptibility
measurements on the coordination compounds of Schiff base, azetidin-2-one, thiazolidin4-one, polystyrene-anchored Schiff base. The organization of the Thesis is such that each
Chapter consists of Abstract, Introduction, Experimental, Results and Discussion and
Conclusion. The Appendicies 1, 2, 3, 4 and 5 have been used for the Abbreviations for the
chemical entities, Materials and sources, Analyses and physical measurements, Tables and
Figures respectively used elsewhere. The Synopsis of each Chapter is presented below:
Chapter 1
This Chapter describes the syntheses and characterization of the Schiff base, LH3
(1) derived from the condensation of salicylaldehyde and o-hydroxyphenylurea and its
coordination compounds with Zn(II), Co(II), Ni(II), Fe(III) and Zr(OH)2(IV) ions. The
nucleophilic addition reaction followed by the elimination of one H2O molecule between
salicylaldehyde and o-hydroxyphenylurea in equimolar ratio in MeOH results in the
formation of 1. A MeOH solution of the latter reacts with a MeOH solution of Zn(II),
Co(II), Ni(II), Fe(III) and Zr(OH)2(IV) ions in equimolar ratio
and
forms
[Zn(LH)(MeOH)] (2), [M(LH)(MeOH)2]2 (3, M = Co, Ni), [FeCl(LH)(MeOH)]2 (4) and

[Zr(OH)2(LH)(MeOH)2] (5) respectively. The coordination compounds are insoluble in
H2O, MeOH and EtOH but soluble in DMF and DMSO. They have been characterized on
the basis of elemental analyses, molecular weight, spectral (IR, reflectance, 1H NMR)
studies, thermo-gravimetric analyses and the magnetic susceptibility measurements. Their
molar conductance values (M = 4.58.2 mho cm2 mol-1 in DMF) show that they are nonelectrolytes. The molecular weight measurements indicate a monomeric structure of 2 and
5, while a dimeric structure of 3 (M = Co, Ni) and 4. The loss of the coordinated MeOH
molecule(s) occur between 80-120 oC in 2-5. LH3 acts as a dibasic tridentate ONO donor
ligand. The (MO) and (MN) stretches occur between 540-570 and 420-450 cm-1
respectively. The reduction of Racah parameter [from the free ion values: 971 cm-1 to
780.7 cm-1 for Co(II) and from 1030 cm-1 to 799.8 cm-1 for Ni(II)] and the values of %
covalency in 3 [19.5 when M = Co(II) and 23.0 when M = Ni(II)] are indicative of
covalent nature of these coordination compounds. 1 exhibits multiplet at 6.82-8.00 ppm
ii
due to the aromatic protons, a singlet at 7.32 ppm due to the azomethine proton, a broad
signal at 10.91 ppm due to the phenolic proton and a singlet at 11.73 ppm due to the
NH proton. The appearance of alcoholic proton (singlet, 1H) at 2.74 ppm and methyl
protons at 3.58 ppm in 2 confirms the presence of coordinated MeOH. The reduced
magnetic moments of 3 (M = Co, Ni) and 4 may be due to the magnetic interaction
between the two metal ions connected by phenoxo bridge. A tetrahedral geometry to 2, an
octahedral geometry to 3 (M = Co, Ni) and 4 and a pentagonal-bipyramidal geometry to 5
have been assigned. The energy optimized structures, 6 and 7 for 1 and 2 respectively are
proposed using the semiempirical ZINDO/1 quantum mechanical calculations.
Chapter 2
This Chapter describes the syntheses of the azetidin-2-one, L'H3 (8) [obtained by
the cyclocondensation of 1 with chloroacetyl chloride (ClCH2COCl, CAC) in the presence
of triethylamine (Et3N) in dioxane]. A MeOH solution of Cu(II), Cd(II), Mn(II), Fe(III)
and MoO2(VI) ions reacts with 8 in 1:1 molar ratio and forms the monomeric coordination
compounds, [Cu(OAc)(L'H2)] (9), [Cd(OAc)(L'H2)] (10), [Mn(OAc)(L'H2)(MeOH)2] (11),
[FeCl2(L'H2)(MeOH)] (12) and [MoO2(acac)(L'H2)(MeOH)] (13) respectively. The
coordination compounds have been characterized on the basis of elemental analyses,
molar conductance, molecular weight, spectral (IR, reflectance and ESR) studies and
magnetic susceptibility measurements. They are insoluble in H2O, MeOH, EtOH but
soluble in DMSO and DMF. They are non-electrolytes in DMF (M = 5.3-8.3 mho cm2
mol-1). 8 behaves as a monobasic tridentate ONO donor ligand. The acetato ligands are
bonded to the central metal ions in a monodentate fashion in 9, 10 and 11. The ESR
spectral parameters of 9 [g|| (2.8) > g (2.08) > 2.0), A|| (1.50 10-2 cm-1, A = 3.0 10-3
cm-1) and G (3.50)] are typical of a tetragonal type geometry. The magnetic moments,
1.87, 5.81 and 5.78 B.M. for 9, 11 and 12 respectively account for their magnetically
dilute nature. A square-planar structure for 9, a tetrahedral structure for 10, the octahedral
structures for 11 and 12 are proposed. The coordination number of Mo is eight in 13.
Chapter 3
This Chapter deals with the syntheses and characterization of a thiazolidin-4-one,
L'H3 (14) [obtained by the cycloaddition reaction of LH3 (1) with mercaptoacetic acid
(HSCH2COOH) in dry C6H6] and its coordination compounds with Cu(II), Co(II), Ni(II),
iii
MoO2(VI) and Zr(OH)2(IV) ions. 14 reacts with appropriate metal ions in 1:1 molar ratio
in MeOH and produces the compounds, [Cu(OAc)(L'H2)] (15), [M(OAc)(L'H2)(MeOH)2]
(16, M = Co, Ni), [MoO2(acac)(L'H2)(MeOH)]
(17) and [Zr(OH)3(L'H2)] (18). The
coordination compounds are air-stable, insoluble in H2O, MeOH, EtOH and soluble in
DMSO and DMF. They are non-electrolytes (M = 4.3-9.6 mho cm2 mol-1) in DMF. 14
behaves as a monobasic tridentate ONO donor ligand coordinating through its phenolic O
(o-aminophenol moiety), N (o-aminophenol moiety) and O (thiazolidin-4-one moiety)
atoms. The phenolic O (aldehydic moiety), N and S atoms (thiazolidin-4-one moiety) are
not involved in coordination. The appearance of two new bands between 1564-1572 cm-1
[as(OAc)] and 1340-1352 cm-1 [s(OAc)] stretches indicates the presence of the
coordinated acetato group in 15 and 16 (M = Co, Ni). The presence of coordinated MeOH
molecule(s) in 16 (M = Co, Ni) and 17 is proposed on the basis of IR spectral studies. The
reflectance spectra of 15 and 16 (M = Co, Ni) are consistent with square-planar and
octahedral environment around metal ions. 14 exhibits the signals at 6.82-8.00, 7.32,
10.91 and 11.7 ppm due to the aromatic, azomethine, OH protons, andNH protons
respectively. A square-planar structure for 15, an octahedral structure for 16 (M = Co, Ni)
and 18 are proposed. Mo assumes a coordination number of eight in 17.
Chapter 4
This Chapter deals with the syntheses and characterization of polystyrene-anchored
Schiff base, PSCH 2 LH 3 (19) and its coordination compounds. The nucleophilic
addition reaction followed by the elimination of one H2O molecule bet wee n
polyst yr ene-3- for mylsalic ylat e and o- hydro xyphenylur ea in DMF in t he
presence o f et hyl acet at e result s in t he format io n o f 19. T he lat t er reacts
with a DMF swollen suspension of Cu(II), Cd(II), Mn(II), Fe(III) and MoO2(VI) ions and
forms the corresponding polystyrene-anchored coordination compounds, [PSCH 2
LH 2 Cu( OAc)(DMF)] (20), [PSCH 2 LH 2 Cd(OAc)(DMF)] (21), [PSCH 2
LH 2 Mn( OAc)(DMF) 3 ] (22), [PSCH 2 LH 2 FeCl 2 (DMF) 2 ] (23) and [PSCH 2
LH 2 MoO 2 (acac)]
(24,
acacH
pent ane-2,4-d io ne)
respect ively. The
polystyrene-anchored coordination compounds (20-24) have been characterized on the

basis of elemental analyses, spectral (IR, reflectance, ESR) studies and magnetic
susceptibility measurements. The per cent reaction conversion (PRC) of the compounds
iv
lies between 44.8-81.3 and the metal binding capacity (MBC) of the ligand between 0.320.60 mmol of metal per g of the resin. The coordinated DMF molecules are completely
lost from the polystyrene-anchored coordination co mpo unds by heat ing t hem at a
definit e t emper at ure in an air-o ven fo r 3 h. 19 acts as a monobasic bidentate ON
donor ligand in these compounds. 20 shows usual anisotropic pattern with two g values,
which are characteristic of axial symmetry. 2 0, 22 and 23 are paramagnetic and
magnetically dilute. A square-planar structure for 20, a tetrahedral structure for 21and the
octahedral structures for 22, 23 and 24 are proposed.
INTRODUCTION
1
The Introductory Part of the Thesis entitled Studies on the Metal Complexes of
First and Second Transition Series consists the Literature Survey on the coordination
compounds of Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Zr(OH)2(IV), MoO2(VI) and
Cd(II) ions. A metal coordination compound is the aggregate of Lewis acid (electron pair
acceptor central metal atom or metal ion having vacant d- or f- orbitals) and Lewis base(s)
(electron pair donor anion, cation or neutral entity). A brief summary of the coordination
compounds of the above metal ions with monodentate, bidentate, tridentate, tetradentate
and polydentate ligands are presented here.
Coordination compounds of manganese(II)

Mangnese (Mn) is a greyish-white transition metal belonging to Group 7 and
Period IV of the Periodic Table. Its atomic number, atomic weight and the electronic
configurations are 25, 54.93 amu and [Ar] 4s23d5 respectively. Its common oxidation
states are +2, +3, +4, +6 and +7. Mn ions have various colours depending upon their
oxidation state and they are generally paramagnetic. The most stable oxidation state of Mn
is +2, which has pink to red colour. Mn(II) ion acts as a cofactor for a number of enzymes
in higher organisms, where they are essential in detoxification of superoxide free radicals.
It is an essential trace nutrient in all forms of life. The ability of Mn(II) ion to form the
coordination compounds with a wide range of ligands has been reported. These ligands are
coordinated to Mn(II) ion in a monodentate, bidentate, tridentate, tetradentate,
pentadentate and hexadentate fashion. We present here a brief survey of the Chemistry of
coordination compounds of Mn(II) ion.
A.
With monodentate ligands:

The synthesis of centrosymmetric compound, bis[-(E)-1,5-dimethyl-2-phenyl-4-
(3-pyridylmethyleneamino)pyrazol-3(2H)-one]bis{dibromido[(E)-1,5-dimethyl-2-phenyl4-(3-pyridylmethyleneamino)pyrazol-3(2H)-one]manganese(II)}, [Mn2Br4(C17H16N4O)4]
has been reported[1]. In the crystal structure, the Mn atom adopts a trigonal-bipyramidal
geometry and the ligand adopts two coordination modes, monodentate and bidentate
bridging.
2
B.
With bidentate ligands:

Maurya et al.[2] have synthesized a reddish-brown, non-electrolyte (M = 10.5 mho
cm2 mol-1), four-coordinate compound, [Mn(OAc)L(H2O)] (where LH = 25; R = 3-OMe,

R' = OH, R'' = H) by refluxing a mixture of an EtOH solution of Mn(OAc)24H2O and a
DMF solution of LH in 1:1 molar ratio for 4 h. It decomposes at 260 oC. It is soluble in
DMF and DMSO. LH behaves as a monobasic bidentate ON donor ligand coordinating
through its phenolic O and azomethine N atoms. The acetato ligand is coordinated to the
metal ion in a monodentate fashion. The (MnO) and the (MnN) vibrations occur at
510 an 435 cm-1 respectively. Its magnetic moment is 5.94 B.M.
The six-coordinate heterochelate, [MnL2L'] [here LH = 25, R = 5-Cl, 5-Br; R' =
OH; R'' = H; L' = 26, R = R' = H; R'' = Me; R''' = (CH2)2] has been synthesized[3]. LH acts
as a monobasic bidentate ON donor ligand coordinating through its phenolic O and
azomethine N atoms, whereas L' acts as a neutral NN donor ligand coordinating through
its azomethine N atoms. The heterochelates exhibit three weak bands at ~15000, ~19000
and ~25500 cm-1 due to the 6A1g 4T1g(G)(1), 6A1g 4T2g(G)(2) and 6A1g 4A1g(G)(3)
transitions respectively for octahedral geometry. The magnetic moments of the
heterochelates are 6.00 and 6.01 BM.respectively. The heterochelates show higher
antimicrobial activity against S. typhi, F. oxysporum, S. cereusisae and L. theobromae than
LH. The enhanced antimicrobial activity of the heterochelates against these microbes is
due to the presence of two halogen and four azomethine groups. An octahedral structure
(27, R = 5-Cl, 5-Br; M = Mn) has been suggested for the heterochelates.
The reaction of 2-aminophenol with Mn(II) ions in 1:1 molar ratio produces the
aminophenolate compound as precipitate (in solution), which on further treatment with
4-benzyloxybenzaldehyde or but-2-enal in the above molar ratio yields the six-coordinate,
orange-yellow compound, [MnL2(H2O)2] or brown compound, [MnL'2(H2O)2] respectively
(where LH and L'H = 28 and 29 respectively)[4]. They melt at 180 and 200 oC respectively.
They display two bands one at 16667, 16393 cm-1 and another at 20704, 20000 cm-1
respectively indicating the presence of an octahedral environment around the metal ion.
They exhibit the magnetic moments 5.94 and 5.78 B.M. respectively, corresponding to
high-spin octahedral symmetry due to five unpaired electrons. The coordination
compounds are more biologically active against S. dysenteria, E. coli (responsible for
3
diarrhoea), P. aeruginosa, B. subtilis (responsible for contamination), S. lutea and S.
aureus (responsible for wound infection) than 2-aminophenol.
Due to the formation of stable coordination compounds with heavy metal ions,
aroylhydrazones have been employed as specific reagents in analytical and extraction
chemistry[5]. A red, four-coordinate compound, [Mn(LH)2] (where LH2 = 30, R = H) is
obtained when an EtOH solution of LH2 and Mn(OAc)24H2O in 2:1 molar ratio are
refluxed in the presence of TEM[6]. It decomposes at 274 oC and its molar conductance is
43 mho cm2 mol-1. LH2 acts as a monobasic bidentate ON donor ligand coordinating
through its enolic O and azomethine N atoms.
C.
With tridentate ligands:

A monomeric, dark-brown, six-coordinate, polystyrene-anchored coordination
compound, [PSLMn(DMF)3] (here PSLH2 = 31) is obtained[7] by refluxing a DMF

swollen suspension of Mn(OAc)24H2O and PSLH2 for 8 h. The Schiff base acts as a
dibasic tridentate ONO donor ligand. The DMF molecules are coordinated to the metal
ion. The PRC of the compound is 78.6. The MBC of the ligand is 0.60 mmol of metal per
g of it. Its magnetic moment is 5.92 B.M. It displays three bands at 18440, 22980 and
25220 cm-1 due to the 6A1g 4T1g(G), 6A1g 4T2g(G) and 6A1g 4A1g(G) spin-forbidden
transitions respectively.
The heterochelates containing O and N atoms are important owing to their
significant antifungal, antibacterial and anticancer activity. The pale-brown compound,
[Mn5Cl10(LH2)(H2O)9] and the black heterochelate, [Mn2Cl3(LH2)(acac)(H2O)] (where
LH2 = 32) have been synthesized[8]. They are non-electrolytes. The ligand acts as a
neutral tridentate ONO donor. The central Mn(II) ions in both the cases are held together
by bridged chloro ligands and the remaining coordination sites are occupied by O atom of
water molecules. The appearance of three bands at 25640, 22222, 17240 and 25315,
20833, 16805 cm-1 and the low magnetic moments (2.5 and 3.1 BM) respectively of the
compound/ heterochelate due to super-exchange suggest their octahedral geometry around
the metal ions.
A
dark-brown,
six-coordinate,
polystyrene-anchored
compound,
[PSCH2LMn(DMF)3] (where PSCH2LH2 = 33; R = 3-PSCH2OCO, X = O) has been

synthesized by refluxing Mn(OAc)24H2O and the ligand in 2:1 molar ratio in DMF[9]. The
4
Schiff base acts as a dibasic tridentate ONO donor ligand coordinating through its
phenolic O, azomethine N and enolic O atoms. The furanoic O atom does not participate
towards coordination as evident by the unaltered (COC) stretch (1080 cm-1) both in
ligand and the compound. Its magnetic moment is 5.85 B.M. The appearance of two bands
one at 16395 cm-1 and another at 24600 cm-1 due to the 6A1g 4T1g(G) and 6A1g 4T2g(G)
transitions is indicative of an octahedral environment around the metal ion.
Kumar et al.
[10]
have synthesized a dark-brown, polystyrene-anchored six-
coordinate compound, [PSCH2LHMn(DMF)3] (where PSCH2LH3 = 34) by refluxing a

DMF swollen suspension of PSCH2LH3 and a DMF solution of Mn(OAc)24H2O. The
PRC of the compound is 93.3 and the MBC of PSCH2LH3 is 0.58 mmol of Mn per g of
the ligand. PSCH2LH3 behaves as a dibasic tridentate ONO donor ligand. The magnetic
moment (5.9 B.M.) and the appearance of two bands one at 16000 and another at 22500
cm-1 due to the 6A1g 4T1g(G) and 6A1g 4T2g(G) transitions respectively indicate an
octahedral environment around the metal ion.
A deep-brown, binuclear, six-coordinate compound, [Mn2L2(H2O)4] is obtained by
stirring an EtOH solution of Mn(OAc)24H2O and LH2 (35A-35C) in 1:1 molar ratio in the
presence of LiOH for 4 h[11]. It melts at 198 oC. It is soluble in Me2CO but insoluble in
MeOH. The ligand behaves as a dibasic tridentate OON donor. The lower value of the
magnetic moment (5.39 B.M.) indicates the presence of an anti-ferromagnetic interaction
between the adjacent metal cations. An octahedral geometry 36 (M = Mn; A = H2O) has
been suggested for the compound.
The synthesis of a light-yellow, four-coordinate, non-electrolyte (in DMSO),
[MnCl(LH)]3H2O (where LH2 = cephalexin, 37) has been reported[12]. It is air-stable,
soluble in DMSO and DMF, slightly soluble in MeCN. The coordination of the ligand
occurs through the carboxylato O, carbonyl O (-lactam) and N atom of NH2 group. The
carboxylato group is coordinated in a monodentate mode ( = 235 cm-1). A mass loss
equivalent to three water molecules in the 90-110 oC range suggests that these molecules
are not coordinated to the metal ion. The magnetic moment (5.6 B.M.) indicates the
presence of five unpaired electrons. A tetrahedral structure (38, M = Mn) has been
assigned to it.
5
A four-coordinate compound, [MnCl(LH)]3H2O (here LH2 = 39) has been
synthesized by stirring a MeOH solution of NaHL and MnCl24H2O in 2:1 molar ratio
for 8 h at room temperature[13]. It is air-stable, soluble in DMSO and DMF and slightly
soluble in MeCN. The (C==O)(-lactam) stretch of the ligand occurring at 1780 cm-1
shifts to 1720 cm-1 in the coordination compound indicating the involvement of carbonyl
O atom towards coordination. The overlapped (C==O)(amide) and (C==O)(ester) bands
in LH2 appears at 1640 cm-1. These bands remain unchanged in the compound suggesting
that coordination of the ligand occurs through the O atom from the lactam carbonyl group
rather than the amide and ester carbonyl groups. The carboxylato group is coordinated in a
monodentate mode ( = 240 cm-1). The amino group of LH2 is coordinated to the metal
ion as evident by the presence of the (MnN) stretch at 450 cm-1. Thus, LH2 behaves as
a monobasic tridentate OON donor ligand. The compound has a magnetic moment of 5.4
B.M. It shows higher activity than LH2 against P. mirabilis, K. pneumoniae, S. enteriditis
and E. coli, while it remains inactive towards S. aureus and P. aeruginosa. A tetrahedral
structure (40, M = Mn) has been assigned to it.
Hankare et al.[14] have synthesized a brown, dimeric, four-coordinate, nonelectrolyte, high-spin compound, [Mn2Cl2L2] [here LH = 41, the Schiff base obtained
from the condensation of 5-(2'-thiazolylazo)salicylaldehyde and 4-methoxyaniline] by
refluxing an EtOH solution of MnCl24H2O and LH in 1:1 molar ratio. It is soluble in
DMSO. The Schiff base acts as an ONN donor ligand coordinating through its phenolic O
and azomethine N to one Mn(II) ion and through azo N atom to another Mn(II) ion.
Upon digesting an aqueous solution of Mn(OAc)24H2O and a DMF solution of LH
(42; R = Me, R' = Ph) in 1:1 molar ratio for h, a six-coordinate compound, [MnL2] is
obtained[15]. It is insoluble in common organic solvents but sparingly soluble in dioxane
and DMF. The monobasic ligand coordinates to the metal ion through its pyrazolinic O,
azomethine N and thiazolic N atoms. The (MnO) and (MnN) vibrations occur at
460 and 390 cm-1 respectively in the coordination compound. Due to their doubly
forbidden nature, it exhibits three very low intense bands at 16667, 23256 and 26316 cm-1
due to the 6A1g 4T1g(G), 6A1g 4T2g(G) and 6A1g 4Eg(G)/4A1g(G) transitions
respectively indicating the octahedral environment around metal ions. The magnetic
moment (6.05 B.M.) suggests its distorted octahedral geometry alongwith high-spin 3d5
6
configuration of the metal ion. The ligand and the coordination compound show
antibacterial activity against E. coli, B. subtilis and S. aureus.
Chandole et al.[16] have synthesized the air-stable, non-hygroscopic, nonelectrolyte, dimeric, six-coordinate compound, [MnClL(H2O)]2 (here LH = 43; R = Me,
Et, propyl) and [MnCl(L'H)(H2O)]2 (here L'H2 = 43; R = CH2CH2OH) by refluxing a
MeOH solution of MnCl22H2O and LH or L'H2 in 1:1 molar ratio for 4 h. They are
soluble in DMF and DMSO. The coordinated water molecules are lost between 190-200
o
C. Although L'H2 is potentially a dibasic tetradentate NONO donor ligand but similar to
LH, it also behaves as a monobasic tridentate NON donor ligand bridging through its
enolic O atom. The coordination compounds display three bands between 16835-16949,
~23584 and ~26385 cm-1 due to the 6A1g 4T1g(G)(1), 6A1g 4T2g(G)(2) and 6A1g
4
Eg(G)(3) transitions respectively indicating the octahedral environment around the metal
ion. Their magnetic moments lie between 4.88-5.07 B.M. The compound (when R = Me)
crystallizes in a monoclinic fashion with a = b = 4.92 , c = 5.41 , = = 90, = 120.
They exhibit higher antifungal activity against A. niger than the corresponding ligands. A
distorted octahedral structure (44, M = Mn) has been suggested for them.
On refluxing an hot MeOH solution of Mn(NO3)26H2O and LH (45) in 1:2 molar
ratio at pH = 7.5-8.5, a brown, six-coordinate complex, [MnL2] is obtained[17]. The
complex is non-electrolyte (M = 10.02 mho cm2 mol-1 in DMSO). LH acts as a
monobasic tridentate ONN donor ligand coordinating through its phenolic O and both
azomethine N atoms. The magnetic moment (5.7 B.M.) and the appearance of the bands at
16611, 24390 and 26881 cm-1 due to the 6A1g 4T1g(G), 6A1g 4T2g(G) and 6A1g 4Eg
transitions respectively indicate the presence of an octahedral environment around the
metal ion. The complex crystallizes in monoclinic fashion with a = 14.223 , b = 5.196
, c = 7.754 . The compound shows higher antimicrobial activity against Gram-negative
E. coli, Gram-positive S. aureus and LH.
The coordination compounds of Schiff bases containing S atom have received
considerable attention during recent past, primarily due to the remarkable antitumor,
antibacterial and antiviral properties[18,19]. The complexation of yellow colored
benzothiazoline derivative, 3-(2,3-dihydro-1,3-benzothiazole-2-yl)quinoxalin-2(1H)-one
(LH2 = 46A, 46B) with Mn(II) ion proceeds with the rearrangement of benzothiazoline
7
ring to form the corresponding red colored, non-electrolyte, [Mn(LH)(OAc)(H2O)2][20]. In
the presence of Mn(II) ion, the benzothiazoline rearranges to form the Schiff base (LH2).
The latter coordinates in keto form as monobasic tridentate ONS donor. The magnetic
moment (5.80 B. M.) and the existence of the bands at 24814, 23529 and 21413 cm-1 due
to the 6A1g 4T1g(G), 6A1g 4T2g(G) and 6A1g 4Eg transitions respectively, are indicative
of an octahedral environment around the Mn(II) ion. The loss of coordinated water
molecules occurs between
150-200 oC.
Makode et al.[21] have synthesized a light-green, dimeric, six-coordinate
compound, [MnL(H2O)2]2 (where LH2 = 47) by refluxing Mn(OAc)24H2O and LH2 in
EtOH. Although LH2 is potentially a dibasic pentadentate ONNSS donor ligand, but
behaves as a dibasic tridentate ONS donor ligand. The phenolic O, azomethine N and the
thioenolic S afford the coordination sites of the octahedron. The value of magnetic
moment (5.14 B.M.) and the appearance of three bands due to the 6A1g 4T1g, 6A1g 4T2g
and 6A1g 4A1g transitions indicate its octahedral stereochemistry. Both the coordinated
H2O molecules are lost between 160-210 oC. It shows activity against E. aureus, P.
mirabilis and S. typhi.
An aqueous solution of Mn(OAc)24H2O reacts with an EtOH solution of LH2 (48)
in 1:2 molar ratio and forms[22] a yellow compound, [Mn(LH)2]. It is stable in air,
decomposes at 201 oC, insoluble in EtOH, C6H6 and CHCl3 but soluble in Me2CO, DMF
and DMSO. It is non-electrolyte in DMSO and Me2CO. LH2 acts as a monobasic tridentate
ONS donor ligand. The (MnN) vibrations occur at 565 cm-1 in the compound. The
magnetic moment (5.9 B.M.) indicates the presence of high-spin octahedral environment
around the metal ion. The compound assumes a six-coordinate structure (49, M = Mn).
A four-coordinate, air-stable, non-electrolyte (in DMSO), [MnCl(LH)] (where LH2
= cephalothin, 50; R = H, R' = Me) has been synthesized by stirring a MeOH solution of
MnCl24H2O and LH2 in 1:2 molar ratio[23]. It is soluble in DMSO and DMF, slightly
soluble in MeCN and insoluble in MeOH and H2O. The (C==O)(-lactam) stretch of LH2
shifts from 1730 to 1690 cm-1 in the compound indicating the involvement of O atom
towards coordination. The (C==O)(amide) stretch of LH2 occuring at 1650 cm-1 remains
unchanged in the compound indicating its non-involvement towards coordination. The
8
as(COO) and s(COO) stretches of LH2 occurring at 1620 and 1400 cm-1 shift to 1615 and
1380 cm-1 respectively in the compound indicating monodentate behaviour of the
carboxylato group ( = 235 cm-1). LH2 acts as a monobasic tridentate OOS donor ligand.
The presence of MS stretch indicates the coordination through thiophene S atom. The
value of magnetic moment (5.5 B.M.) indicates the presence of five unpaired electrons. It
shows a very weak absorption band at 25640 cm-1 due to a spin-orbit forbidden transition.
It shows antibacterial activity higher than the ligand against S. aureus, E. coli, S.
enteriditis and P. mirabilis, while it shows no activity against K. pneumoniae. A
tetrahedral structure (51; R = H, R' = Me, M = Mn, A = nil) has been assigned to it.
An EtOH solution of MnCl24H2O and LH [here LH = 52, R = (C5H4N)CH, R' =
NH C6H4(4-OMe); L'H = 52, R = (C5H4N)CH, R' = NHCH2CH2C6H5; L''H = 52, R =
(C5H4N)CH, R' = N(Me)C6H5; X = S] in 1:2 molar ratio upon refluxing[24] produce brownorange,
six-coordinate,
non-electrolyte,
[MnL2]H2OEtOH,
[MnL'2]3H2O,
[MnL''2]3H2O; brown, six-coordinate, 1:1 electrolyte, [MnL(LH)](OAc) and brown, sixcoordinate, 1:2 electrolyte, [Mn(L''H)2](SCN)2MeOH. The ligands behave as a monobasic
tridentate NNS donors in [MnL2]H2OEtOH, [MnL'2]3H2O, [MnL''2]3H2O; neutral
tridentate NNS donor in [Mn(L''H)2](SCN)2MeOH and neutral as well as monobasic
tridentate NNS donor in [MnL(LH)](OAc). The magnetic moments are 6.02, 5.33, 5.56,
5.62
and
5.81
B.M.
for
[MnL2]H2OEtOH,
[MnL'2]3H2O,
[MnL''2]3H2O,
[MnL(LH)](OAc) and [Mn(L''H)2](SCN)2MeOH respectively. A broad band at 22936,

23419, 23148, 23810 and 23542 cm-1 due to the 6A1g 4T2g(G) transition and a very
week band at 18248, 18903, 18867, 18051 and 18478 cm-1 due to the 6A1g 4T1g(G)(2)
transition respectively occur in
[MnL(LH)](OAc)
and
[MnL2]H2OEtOH, [MnL'2]3H2O, [MnL''2]3H2O,
[Mn(L''H)2](SCN)2MeOH
respectively.
[MnL2]H2OEtOH
crystallizes in a monoclinic fashion with a = 15.164 , b = 18.793 , c = 11.896 ; =

= 90.0o, = 109.31o and Z = 8. An octahedral geometry is assigned to them.
D.
With tetradentate ligands:

Kumar et al.[25] have become the first to synthesize a polystyrene-anchored
asymmetric Schiff base, PSCH2LH2 [53; R = R' = Me, R'' = (CH2)2] and its brown, sixcoordinate compound, [PSCH2LMn(DMF)2]. The Schiff base acts as a dibasic
tetradentate ONNO donor ligand. The magnetic moment of the compound (5.92 B.M.) and
9
the occurrence of two bands one at 16950 cm-1 and other at 24400 cm-1 are characteristic
of its octahedral geometry around Mn(II) ion.
Hasnain et al.[26] have reported the two step syntheses of Mn chelated
polyurethane containing LH2 (54) as the Schiff base. In the first step, a DMSO solution of
LH2 refluxed with Mn(OAc)24H2O in DMSO forms a mustard coloured complex,
[MnL(H2O)2]. In the second step, the polyaddition of toluene-2,4-diisocyanate with
[MnL(H2O)2] is carried out in the presence of di-n-butyltindilaurate. The ligand behaves as
a tetradentate ONNO donor in both the compounds coordinating through its phenolic O
and N atoms of thiosemicarbazide moieties. The high-spin octahedral polymeric complex
(5.68 B.M.) displays three bands at 16200, 19400 and 22980 cm-1 due to the 6A1g 4T1g,
6
A1g 4T2g and 6A1g 4A1g spin-forbidden transitions respectively. The antimicrobial
studies show that metal chelated polyurathane is more active than [MnL(H2O)2].
A four-coordinate, air-stable compound, [MnL] (where LH2 = 55) has been
synthesized by refluxing a MeOH solution of Mn(OAc)24H2O and a CH2Cl2 solution of
LH2 in 1:1 molar ratio for 17 h[27]. It is readily soluble in DMF, DMSO and CHCl3,
sparingly soluble in MeOH and EtOH and insoluble in non-polar solvents. The IR data are
indicative of the dibasic tetradentate ONNO donor nature of the ligand. The compound
shows magnetic moment of 1.9 B.M. indicating the presence of one unpaired electron.
A brown, six-coordinate, monomeric compound, [Mn(LH2)(H2O)2] (where LH4 =
56) has been synthesized[28]. LH4 acts as a dibasic tetradentate ONNO donor ligand. The
coordinated H2O molecules are lost at about 170 oC. The magnetic moment of the
compound is 5.62 B.M.
A brown, low-spin, six-coordinate compound, [Mn(LH2)(H2O)2] (where LH4 =
57) is obtained by stirring MnSO4H2O and LH4 in H2O-EtOH solution[29]. Interestingly, a
yellow, high-spin, six-coordinate compound, [Mn(LH2)(H2O)2] is obtained by stirring
MnCl24H2O and ligand in EtOH. The Schiff base behaves as a dibasic tetradentate ONNO
donor ligand in both the compounds. The magnetic moment of the low-spin compound is
1.85 B.M. and it exhibits two ESR signals one at g = 2.03 and another at g = 4.4 at LNT.
The high-spin compound affords the magnetic moment of 5.90 B.M.
A brown, four-coordinate, thermally-stable, binuclear compound, [MnL]2 (where
LH2 = 58) has been synthesized by Maurya et al.[30]. LH2 behaves as a dibasic tetradentate
10
ONNO donor ligand. The magnetic moment (5.74 BM) of the compound is indicative of
high-spin, tetrahedral environment around both Mn(II) ions.
A six-coordinate, non-electrolyte compound, [MnL(H2O)2] [where LH2 = 59) has
been synthesized[31]. LH2 behaves as a dibasic tetradentate ONOO donor ligand
coordinating through its phenolic O, azomethine N, carbonyl O and nitroso O atoms. The
magnetic moment of the compound is 4.30 B.M.
Manjunathan et al.[32] have
synthesized a four-coordinate, 1:1 electrolyte,
[MnL]Cl (where LH = 60) by refluxing LH and MnCl24H2O in EtOH for 1.5 h. LH acts
as a monobasic tetradentate ONNN donor ligand coordinating through its phenolic O, both
azomethine N and anilinic N atoms. The compound shows six hyperfine lines with g|| =
2.0236 and g = 2.004. A square-planar geometry has been suggested to it.
An air-stable, six-coordinate, slightly ionized (M =13.0 mho cm2 mol-1 in DMF)
complex, [MnLCl2]H2O (here L = 61) is obtained by reacting MnCl2 and L in EtOH[33]. L
behaves as a neutral tetradentate N4 donor ligand coordinating through its both azomethine
and pyridyl ring N atoms. The (MCl) vibration occurs at 224 cm-1. The chloro ligands
occupy the axial coordination sites.
The light-brown, cube-shaped crystalline, seven-coordinate dinuclear Mn(II)
complex, [Mn2L2(1,5-dca)2(dca)2]H2O [L = N,N'-ethylenebis(2-benzoylpyridineimine),
dca = dicyanamide] is obtained by refluxing an equimolar mixture of Mn(NO3)2, L and
dca in EtOH[34]. The molar conductances of the complex are 246 and 212 mho cm2 mol-1
in MeOH and MeCN respectively indicating its existence as a 1:2 electrolytes in these
solvents. The complete loss of H2O molecule occurs at ~175 oC and [Mn2L2(1,5dca)2(dca)2] is obtained. Mn2O3 is the end product at 480 oC. L behaves as a neutral
tetradentate N4 donor ligand. The effective magnetic moment of the complex is 8.36 B.M.
The complex crystallizes in an orthorhombic fashion. Two [Mn(II)L] units are doubly
bridged by dicyanamide ligands in a 1,5 pattern. The molecule of the complex possesses a
centre of inversion at the mid point of the line bisecting the adjacent metal centers of the
dimeric unit. The dca ligands are involved in coordination with the metal center via
monodentate and 1,5 bridging patterns. The pentagonal base is provided by five N atoms,
four from L and one from one of the bridging dca moieties. The axial positions are
occupied by a terminal dca and other by the bidging dca moiety. The axial MnN bonds
11
are shorter than the basal MnN bonds. A distorted pentagonal-bipyramidal structure has
been assigned to the complex. The complex is an efficient catalyst for the oxidation of 3,5di-tert-butylcatechol to 3,5-di-tert-butylbenzo- quinone under air in MeOH solution, but is
inactive in MeCN.
E.
With pentadentate ligands:

A five-coordinate compound, [Mn(LH)]2H2O (here Na2LH = ceftriaxone, 62) has
been synthesized by stirring a MeOH solution of Na2LH and MnCl24H2O in 1:1 molar
ratio for 1 h at room temperature[35]. It is air-stable and insoluble in H2O and EtOH, C6H6,
Me2CO, MeCN, Et2O, py, DMF and DMSO suggesting its polymeric nature. Na2LH
behaves as a dibasic pentadentate ONOON donor ligand. The non-coordinated H2O
molecules are lost between 80-110 oC. The magnetic moment of the compound is 6.1 B.M.
It shows higher bactericidal activity than Na2LH against S. sonnei, P. mirabilis and P.
aeruginosa; lesser activity than Na2LH against S. aureus and S. enteritidis. A fivecoordinate structure (63, M = Mn) has been assigned to it.
The
synthesis
of
monomeric,
seven-coordinate
compound,
[Mn(LH2)(H2O)2](ClO4)2 (here LH2 = 64; R = R' = H) has been reported[36]. The Schiff
base acts as a neutral pentadentate SNNNS donor ligand. The Mn ion is ligated to three N
and two S atoms of the ligand forming the pentagonal girdle and O atoms of the water
molecules occupying the apical positions. The ClO4 ions are involved in hydrogen
bonding with the H2O molecules and with the terminal amino groups of the ligand. A
distorted pentagonal-bipyramidal structure [65; M = Mn, A = H2O] has been suggested to
it.
F.
With hexadentate ligands:

Salehzadeh et al.[37] have reported the synthesis of a monomeric, seven-coordinate,
1:1 electrolyte, [MnClL](ClO4) [here L = 66; R = 2-C5H4N]. L acts as a neutral

hexadentate N6 donor ligand. The Mn(II) ion is coordinated to three py and three
asymmetric tripodal amine N atoms. The environment around the Mn(II) ion is distorted
pentagonal-bipyramid.
12
Coordination compounds of iron(III)
Iron (Fe) is a greyish transition metal of Group 8 and Period IV of the Periodic
Table. Its atomic number, atomic weight and the electronic configurations are 26, 55.84
amu and [Ar] 3d64s2 respectively. It is associated with ferromagnetic properties. Its
common oxidation states are +2 and +3. Ferrous ion (Fe2+) is necessary trace element in
living organisms. It is present in hemoglobin, myoglobin, cytochrome system. Iron
containing enzymes usually containing heme prosthetic groups participate in catalysis of
oxidation reactions in biology. The ability of Fe(III) ion to form the coordination
compounds with a wide range of ligands has been reported. These ligands are coordinated
to Fe(III) ion in a bidentate, tridentate, tetradentate, pentadentate and hexadentate fashions.
We present here a brief survey of the Chemistry of coordination compounds of Fe(III) ion.
A.

The synthesis of a brown, high-spin, six-coordinate compound, [FeCl2L(PPh3)2]
(where LH = 25, R = H, C4H4; R' = OH; R'' = H, Cl, Me, OMe) has been reported[38]. The
IR data indicate the monobasic bidentate ON donor behaviour of LH. The compounds
have been used as catalysts in aryl-aryl coupling reactions between phenylmagnesium
bromide and phenyl bromide to yield biphenyl.
The reaction of 2-aminophenol with Fe(III) ions produces the aminophenolate
coordination compound as precipitate (in solution), which on further treatment with
4-benzyloxybenzaldehyde or but-2-enal in 1:1:1 molar ratios yields[4] the deep-brown, sixcoordinate compounds, [FeClL2(H2O)] or [FeClL'2 (H2O)] (where LH and L'H = 28 and 29
respectively). They melt at 290 and 190 oC respectively. Both LH and L'H act as the
monobasic bidentate ON donor ligands. The former displays the (FeO) and (FeN)
vibrations at 600 and 508 cm-1 respectively, while the latter displays these vibrations at
582 and 428 cm-1 respectively. Their magnetic moments (5.97 and 6.00 B.M. respectively)
correspond to the presence of five unpaired electrons in a high-spin octahedral Fe(III)
compound. These values are very close to the spin-only value (5.90 B.M.) since the
ground state (derived from 5S state of free ion) has no orbital angular momentum.
[FeClL2(H2O)] displays the molecular ion peak at 713 (M+) and 302 (100%,
C6H5CH2OC6H4CN==C6H4O)+.
Another
compound,
[FeClL'2(H2O)]
displays
the
molecular ion peak at 429 (M+) and 160 (100%, CH3CHCHCHNC6H4O)+. They are
13
biologically more active against S. dysenteria, E. coli, P. aeruginosa, B. subtilis, S. lutea
and S. aureus than 2-aminophenol.
On refluxing an EtOH solution of FeCl3 (anhydrous) and LH (67) in 1:2 molar
ratio for 2 h, a black dimeric coordination compound, [FeClL2]2 is obtained[39]. It is nonhygroscopic, air-stable, decomposes above 230 oC, soluble in DMF and DMSO but
partially soluble in MeOH, EtOH, MeCN, PhNO2 and CHCl3. It is non-electrolyte in
MeOH and PhNO2. The ligand is coordinated to the metal ion through its phenolic O and
azomethine N atoms. The low value of the magnetic moment (5.3 B.M.) indicates the
bridged structure involving an anti-ferromagnetic exchange interaction. A dimeric
octahedral structure has been suggested for it.
The synthesis of a brown, six-coordinate, polystyrene-anchored coordination
compound, [PSCH2LFeCl2(DMF)2] (here PSCH2LH = 68) has been reported[25]. The
ligand acts as a monobasic bidentate ON donor ligand. The magnetic moment (6.00 B.M.)
and the appearance of three bands at 12200, 15500 and 19000 cm-1 suggest an octahedral
geometry around Fe(III) ion.
B.

The dark-brown, six-coordinate, polystyrene-anchored coordination compound,
[PSLFeCl(DMF)2] (where PSLH2 = 31) is obtained by refluxing a DMF swollen

suspension of PSLH2 and anhydrous FeCl3 for 6 h[7]. Its PRC is 93.7. The MBC of the
ligand is 0.73 mmol of metal per g of it. The dibasic tridentate ligand coordinates through
its phenolic O, azomethine N and alcoholic O atoms. The magnetic moment of the
compound is 5.87 B.M. The latter displays three bands at 12720, 19600 and 25000 cm-1
due to the 6A1g 4T1g(G), 6A1g 4T2g(G), 6A1g 4A1g(G) spin-forbidden transitions
respectively suggesting its octahedral geometry.
The brown coloured compound, [Fe3Cl8(LH)(H2O)3]2H2O and the red coloured
[FeL(acac)(H2O)]H2O have been synthesized by reacting FeCl3 and LH2 (32) in the
presence and absence of Et3N respectively[8]. LH2 acts as a monobasic tridentate ONO
donor ligand in the former and as a dibasic tridentate ONO donor ligand in the latter. The
lower value of magnetic moment (3.7 B.M.) for the brown compound is due to the spindensity exchange between the iron(III) centers. The value of magnetic moment (5.9 B.M.)
for the red compound indicates its octahedral geometry. They are more potent fungicides
14
and bactericides than the ligand. A chloro-bridged structure has been suggested for the
brown compound.
A DMF swollen suspension of PSCH2LH2 (33; R = 3-PSCH2OCO, X = O) upon
refluxing with anhydrous FeCl3 produces[9] a brown, six-coordinate compound,
[PSCH2LFeCl(DMF)2]. The Schiff base acts as a dibasic tridentate ONO donor ligand
coordinating through its phenolic O, azomethine N and enolic O atoms. The furanoic O
atom does not participate towards coordination. The magnetic moment (5.98 B.M.) and
the appearance of three bands at 12500, 17420 and 25000 cm-1 due to the 6A1g 4T1g(G),
6
A1g 4T2g(G) and 6A1g 4A1g(G) transitions are indicative of an octahedral environment
around the metal ion.

[10]
Kumar et al.
have synthesized a reddish-brown, polystyrene-anchored, six-
coordinate compound, [PSCH2LHFeCl(DMF)2] (where PSCH2LH3 = 34) by refluxing a

DMF swollen suspension of PSCH2LH3 and a DMF solution of anhydrous FeCl3 The
PRC of the compound is 64.2 and the MBC of PSCH2LH3 is 0.41 mmol of Fe per g of
the ligand. The ligand behaves as a dibasic tridentate ONO donor. The magnetic moment
(5.96 B.M.) and the appearance of three bands at 13000, 17100 and 25100 cm-1 due to the
6
A1g 4T1g (G), 6A1g 4T2g (G), 6A1g 4A1g (G) indicate an octahedral environment

The synthesis of a six-coordinate compound, [FeX2L(H2O)]2H2O (here LH = 69,
X = Cl, NO3) has been reported[40]. LH acts as a monobasic tridentate ONO donor ligand.
[FeCl2L(H2O)]2H2O shows three bands due to the presence of both high-spin Fe(III) (S =
5/2) and low-spin Fe(III) (S = 1/2) ions within the same crystal lattice indicating its
octahedral geometry.
The synthesis of a brown, dinuclear coordination compound, [Fe2L2(NO3)2]H2O
(here LH2 = 70, X = NH2) has been reported[41]. It melts above 280 oC and is soluble in
common organic solvents but partially soluble in DMF and DMSO. LH2 behaves as a
bis(monobasic tridentate) ONN donor ligand. The appearance of two new bands at 1384
and 856 cm-1 indicates the presence of coordinated nitrato group in the compound. The
(FeO) and the (FeN) vibrations occur at 580 and 454 cm-1 respectively. The low
value of magnetic moment (4.95 B.M.) of the compound suggests the presence of an anti-
15
ferromagnetic interaction acting between the neighbouring Fe(III) ions. The lattice H2O
molecules are lost by heating the compound between 40-97 oC.
The brown, six-coordinate complex, [FeL2](NO3) (here LH = 45) is obtained[17] on
refluxing an hot MeOH solution of Fe(NO3)39H2O and LH in 1:2 molar ratio at pH = 7.58.5. LH acts as a monobasic tridentate ONN donor ligand coordinating through phenolic O
and both azomethine N atoms. The magnetic moment (5.85 B.M.) and the appearance of
three bands at 12658, 18940 and 30864 cm-1 due to the 6A1g 4T1g(G), 6A1g 4T2g(G)
and 6A1g 4A1g(G) transitions respectively indicate the presence of an octahedral
environment around the metal ions. The compound shows higher antimicrobial activity
against Gram-negative E. coli, Gram-positive S. aureus and LH.
A reddish-brown, six-coordinate, dinuclear compound, [Fe2Cl4(LH)2]2EtOH (here
LH2 = 35A-35C) is obtained by stirring an EtOH solution of FeCl36H2O and LH2 in 1:2
molar ratio for 4 h[11]. It melts at 160 oC. It is soluble in MeOH but insoluble in H2O and
Et2O. The rather higher value of molar conductance (M = 58.0 mho cm2 mol-1) in DMF is
due to the partial replacement of the chloro ligands with DMF molecules. The IR data are
indicative of the monobasic tridentate OON donor behaviour of the ligand. The compound
shows two broad bands one at 18797 cm-1 and other at 25510 cm-1 due to the spinforbidden
A1 4T2(G) and 6A1 4A1, 4E(G) transitions respectively. Its magnetic
moment is 5.94 B.M. and that of a single Fe(III) ion is 4.20 B.M. Thus, there occurs an
anti-ferromagnetic interaction between the adjacent Fe(III) ions. The unsymmetrical broad
band at g = 1.827 indicates a distorted octahedral geometry around the Fe(III) ions. The
compound consists of two mononuclear units, where the cations in each unit are
coordinated to OON sites of a ligand and are linked together by Cl atoms. An octahedral
structure (71) has been assigned to it.
A non-electrolyte, five-coordinate compound, [FeCl2(LH)]3H2O (72) (here LH2 =
39) has been synthesized by stirring a MeOH solution of NaHL and FeCl36H2O in 2:1
molar ratio for 8 h at room temperature[42]. It is air-stable, soluble in DMSO and DMF and
slightly soluble in MeCN. NaHL behaves as a monobasic tridentate OON donor ligand.
The carboxylato group coordinates in a monodentate fashion. The compound has a
magnetic moment of 4.6 B.M. which lies between the values expected for the Fe(III)
coordination compounds with S = 5/2 and S = 1/2 suggesting the possibility of spin-state
16
equilibrium between 6A2 and 2T2 states respectively. It shows weak absorption at 23810
cm-1 due to the spin-orbit forbidden transitions. The latter shows higher bactericidal
activity than LH2 against P. mirabilis, K. pneumoniae, S. enteriditis and E. coli, while it
remains inactive towards S. aureus and P. aeruginosa.
A four-coordinate, 1:1 electrolyte (in DMSO), [FeCl(LH)]Cl (where LH2 =
cefoxitin, 50; R = OMe, R' = NH2) has been synthesized by stirring a MeOH solution of
NaHL and FeCl36H2O in 1:1 molar ratio for 8 h in N2 atmosphere at room temperature[43].
It is air-stable, soluble in DMF and DMSO but slightly soluble in MeCN. NaHL behaves
as a monobasic tridentate OOS donor ligand. The carboxylato group coordinates in a
monodentate mode. The presence of (MS) stretch at 300 cm-1 indicates coordination
through S atom of thiophene moiety. Its magnetic moment is 6.1 B.M. It shows lesser
bactericidal activity than LH2 against S. aureus, E. faecalis, E. coli, P. mirabilis, S. sonnei
and S. enteritidis.
El-Sawaf et al.[44] have reported the synthesis of a brown, five-coordinate
compound, [Fe(ClO4)2L] [where LH = 73].
LH coordinates through carbonyl O
(pyrazolone ring), thiolato S and azomethine N atoms. The chlorato group coordinates in a
monodentate fashion. The magnetic moment of the compound is 3.7 B.M. A squarepyramidal structure has been suggested for the latter.
C.

Kumar et al.[25] have synthesized a reddish-brown, six-coordinate polystyrene-
anchored coordination compound, [PSCH2LFeCl(DMF)] by refluxing a DMF swollen

suspension of PSCH2LH2 [53; R = R' = Me, R'' = (CH2)2] and a DMF solution of
anhydrous FeCl3 in 2:1 molar ratio in the presence of ethyl acetate and Et3N. Its PRC is
49.2. The MBC of the ligand is 0.34 mmol of metal per g of it. The Schiff base acts as a
dibasic tetradentate ONNO donor ligand. The magnetic moment of the compound is 5.94
B.M. The three bands at 12650, 16970 and 25000 cm-1 in the latter are characteristic of
octahedral geometry around Fe(III) ion.
Although LH2 (74) and L'H2 (75) are potentially the dibasic hexadentate
NONNON donor and the dibasic heptadentate NONNNON donor ligands respectively,
they act as a dibasic tetradentate ONNO donors[45] in the black, mononuclear compound,
[FeL1.5]3H2O and another black, binuclear compound, [Fe2L'3]. The former shows a
17
narrow band at 14493 cm-1 in nujol and a broad band at 15748 cm-1 in DMSO, while the
latter shows a narrow band at 14493 cm-1 in nujol and a broad band at 16367 cm-1 in
DMSO due to the spin-forbidden, 6A1g 4T2g(G) transition indicating the distorted
octahedral environment due to the polymerization around the metal ion. Their magnetic
moments are 3.86 and 3.38 B.M. respectively. The former displays gx, gy and gz signals at
2.216, 2.109 and 1.959 respectively, while these signals appear at 2.224, 2.115 and 1.959
respectively in the latter indicating severe distortion of the octahedral geometry in the
array in the solid state.
Saghatforoush et al.[46] have synthesized the six-coordinate, 1:2 electrolyte (M =
196-233 mho cm2 mol-1 in MeCN), [FeL(H2O)2]Cl2 [where LH = 5-R-N-(2pyridylethylsulphanylethyl)salicylideneimine; R = OMe, N2Ph, I, NO2] (76) by refluxing a
MeOH solution of FeCl36H2O and LH in 1:1 molar ratio in the presence of NaOH. They
are light-brown to dark-brown crystalline solids, fairly soluble in MeOH, MeCN, DMF,
DMSO and melt between 173-201 oC. LH coordinates through deprotonated phenolic O,
imine N, thioether S and py N atoms and affording an octahedral geometry around the
Fe(III) ion in the compounds. It decomposes (when R = I) before melting at 209 oC. The
others melt before undergoing exothermic decomposition. They undergo two-step
degradation reactions. The first step occurs at 127, 130, 134 and 135 oC (when R = I,
OMe, NO2, N2Ph) respectively corresponding to the loss of two water molecules. The
second step occurs at 210, 231, 235, 218 oC corresponding to the loss of organic ligand
moiety. The compound (when R = NO2) has got the highest thermal stability. The Schiff
base is more potent antibacterial than the compounds. The antibacterial data indicate high
activity of the ligand (when R = I) against S. pyogenes, S. agalaciae, S. aureus, P.
anthracis, K. pneumoniae and P. aeruginosa.
D.

Relatively little work has been reported on Fe(III) coordination compounds with
pentadentate ligands. A six-coordinate compound, [FeCl(LH)]2H2O (where Na2LH = 62)

has been synthesized by stirring a MeOH solution of Na2LH and FeCl36H2O in 1:1 molar
ratio for 1 h at room temperature[35]. It is air-stable and insoluble in H2O, EtOH, C6H6,
Me2CO, MeCN, Et2O, py, DMF and DMSO. The energy difference ( = 240 cm-1)
between as(COO) and s(COO) stretches suggests the monodentate coordinating
18
behaviour of carboxylato group. Na2HL behaves as a dibasic pentadentate ONOON donor
ligand. The non-coordinated H2O molecules are lost between 80-110 oC. The magnetic
moment of the compound is 5.9 B.M. The latter shows higher bactericidal activity than
Na2LH against P. mirabilis however, it is less active than Na2LH against E. coli, S. aureus,
S. enteritidis and
E.
S. sonnei. An octahedral structure (77) has been assigned to it.

Tweedle et al.[47] have synthesized a monomeric, six-coordinate, 1:1 electrolyte,
[Fe(LH2)]Y (here LH4 = 78, R = H, OMe, NO2; Y = PF6, NO3, BF4, I, Cl). LH4 acts as a
dibasic hexadentate ONNNNO donor ligand. A distorted octahedral geometry has been
suggested for the compounds.
Kannappan et al.[48] have synthesized the monomeric, low-spin, six-coordinate
compounds, [FeL](ClO4), [FeL'](ClO4), [FeL](BF4) and [FeL'](BF4) (here LH2 =
N,N',N'',N'''-1,5,8,12-tetraazadodecanebis(salicylaldiminato) and L'H2 = N,N',N'',N'''1,5,8,12-tetraazadodecanebis(3-methoxysalicylaldiminato). LH2 and L'H2 act as the
dibasic hexadentate ONNONN donor ligands. The coordination geometry around Fe(III)
ion is distorted octahedral with the iron to phenoxo O bonds being trans to each other. In
the crystal lattice, the mononuclear entities are organized into infinite 1D chains due to Hbonding interactions involving the secondary amine residue and one O or F atom of a
counter anion respectively.
Sarkar et al.[49] have reported the synthesis of a monomeric, six-coordinate, 1:1
electrolyte, [Fe(LH2)](ClO4) [here LH4 = 79]. LH4 acts as a dibasic hexadentate ONSSNO
donor ligand.
The syntheses of two monomeric, dark-green, ion-pair coordination compounds,
[FeL][FeCl4] [here LH2 = 1,3-di-(o-salicylaldiminophenylthio)propane] and [FeL'][FeCl4]
[here L'H2 = 1,2-di(o-salicylaldiminophenylthio)xylene] have been reported[50]. Each
Fe(III) ion has a distorted octahedral geometry in the cationic part and a distorted
tetrahedral in the anionic part. The Fe(III) centre in the cationic species is low-spin.
Fe(ClO4)36H2O on reacting with above ligands forms the monomeric, six-coordinate, 1:1
electrolyte, [FeL](ClO4) or [FeL'](ClO4) respectively. The Fe(III) centres in both cationic
species are high-spin. LH2 and L'H2 act as the dibasic hexadentate N2S2O2 donor ligands.
19
Coordination compounds of cobalt(II)
Cobalt (Co) is a hard, grey, d-block transition metal belonging to the Group 9 and
Period IV of the Periodic Table. Its atomic number, atomic weight and electronic
configurations are 27, 58.93 amu and [Ar] 3d74s2 respectively. Its common oxidation
states are +2 and +3. The Co(II) has a d7 system and its coordination compounds show the
paramagnetism either equivalent to three unpaired electrons (Oh or Td ) or equivalent to
one unpaired electron (square-planar). Since the orbital contribution of tetrahedral Co(II)
is much less than that of octahedral coordination compounds, the former have generally
lower values than octahedral compounds This high degree of orbital contribution for
octahedral compounds is due to the three-fold degeneracy of 4T1g ground state. The metal
is the central component of the vitamin B12 (cobalmin) and is associated with some
proteins such as methionine and aminopeptidase. 60Co is used in radiotherapy. The ability
of Co(II) ion to form the coordination compounds with a wide range of ligands is well
known. These ligands coordinate to Co(II) ion in a bidentate, tridentate, tetradentate,
pentadentate and hexadentate fashion. We present here a brief survey of the Chemistry of
coordination compounds of Co(II) ion.
A.

The synthesis of a brown, four-coordinate non-electrolyte (M = 6.9 mho cm2 mol-
), [Co(OAc)L(H2O)] (where LH = 25; R = 3-OMe, R' = OH, R'' = H) has been reported[2].
It decomposes at 270 oC. It is soluble in DMF and DMSO. LH acts as a monobasic

bidentate ON donor ligand. The presence of coordinated H2O molecule is indicated by the
presence of a broad band at 3400 cm-1 in the above coordination compound. The acetato
ligand is coordinated in a monodentate fashion. It shows the (CoO) and (CoN)
vibrations at 510 and 435 cm-1 respectively. The magnetic moment (4.30 B.M.) of the
compound indicates a tetrahedral environment around the metal ion.
The synthesis of a green, high-spin, four-coordinate compound, [CoClL(PPh3)]
(where LH = 25; R = H, C4H4; R' = OH, R'' = H, Cl, Me, OMe) has been reported[38]. The
IR data are indicative of the monobasic bidentate ON donor behaviour of LH. The
magnetic moments of the coordination compounds lie between 1.8-2.3 B.M. in squareplanar environment. They have been used as catalysts in aryl-aryl coupling reactions
between C6H5MgBr and C6H5Br to yield biphenyl.
20
An EtOH solution of CoCl26H2O and LH (80) on refluxing for 2 h in 1:2
molar ratio, a four-coordinate compound, [CoL2] is obtained[51]. LH acts as a monobasic
bidentate ON donor ligand. The magnetic moment (3.58 B.M.) of the compound and the
occurrence of a band at 16366 cm-1 due to the 1A1g
B1g transition support its square-
planar geometry. Its antibacterial activity against bacteria like S. aureus, B. subtilis, E. coli
and the fungus A. niger is higher than LH.
A MeOH solution of Co(OAc)24H2O and LH3 (81; R = OH, R' = H) or L'H4 (81;
R = R' = OH) in 1:2 molar ratio on refluxing for 1 h produce a brown, four-coordinate,
non-electrolyte (M = 8.7 mho cm2 mol-1), [Co(LH2)2]3H2O and another red nonelectrolyte (M = 7.6 mho cm2 mol-1), [Co(L'H3)2]3H2O respectively[52]. Both the
coordination compounds are soluble in DMF, DMSO and THF. The former melts at 295
o
C, while the latter at >300 oC. Both the Schiff bases act as monobasic bidentate ON donor
ligands. The (CoO) and the (CoN) vibrations occur at 475 and 455 cm-1 in
[Co(LH2)2]3H2O, while these occur at 480 and 445 cm-1 in [Co(L'H3)2]3H2O
respectively. The magnetic moments of [Co(LH2)2]3H2O and [Co(L'H3)2]3H2O are 4.38
and 4.33 B.M. respectively suggesting their tetrahedral geometries around the metal ion.
Tumer et al.[53] have observed that an EtOH solution of Co(OAc)24H2O and LH2
(82; R = H, R' = 2-OH, R'' = 3-OMe) or L'H (82; R = R' = H, R'' = 4-NMe2) or L''H2 (82; R
= 3-CMe3, R' = 4-OH, R'' = 5-CMe3) on refluxing in 1:2 molar ratio produce the
compounds, [Co(LH)2]H2O (red-brown), [CoL'2]H2O (dark-red) and [Co(L''H)2]H2O
(red) respectively. They are monomeric, air-stable, non-electrolytes and are soluble in
common polar solvents. Although LH2 and L''H2 are potentially the dibasic tridentate
ONO donor ligands, but similar to L'H, they also act as the monobasic bidentate ON donor
ligands in the respective compounds. The NH and pyridine N atoms do not participate
towards the coordination. These tetrahedral coordination compounds have magnetic
moments 4.13, 4.23 and 4.50 B.M. respectively.
The brown compound, [CoL2(H2O)2] (here LH = 28) and the reddish-brown
compound, [CoL'2(H2O)2] (L'H = 29) have been synthesized by template method[4]. The
reaction of 2-aminophenol with Co(II) ions produces the aminophenolate coordination
compound as precipitate (in solution), which on further treatment with 4benzyloxybenzaldehyde or but-2-enal in 1:1:1 molar ratios yields the desired compounds.
21
[CoL2(H2O)2] and [CoL'2(H2O)2] melt at 245 and 225 oC respectively. Both LH and L'H
act as monobasic bidentate ON donor ligands. [CoL2(H2O)2] displays the (CoO) and
(CoN) vibrations at 596 and 450 cm-1 respectively, while [CoL'2(H2O)2] displays these
vibrations at 580 and 460 cm-1 respectively. [CoL2(H2O)2] exhibits two bands, one at
14577 cm-1 and another at 17094 cm-1, while [CoL'2(H2O)2] exhibits these bands at 14815
and 17241 cm-1 respectively due to the 4T1g(F) 4A2g(2) and 4T1g(F) 4T1g(P)(3)
transitions respectively indicating the octahedral environment around the metal ion. The
magnetic moments of [CoL2(H2O)2] and [CoL'2(H2O)2] are 4.97 and 4.95 B.M.
respectively favouring the presence of three unpaired electrons of Co(II) ion in a high-spin
octahedral compound. The higher values than the spin-only value (3.89 B.M.) is due to the
orbital contribution. Their biologically activity against S. dysenteria, E. coli, P.
aeruginosa, B. subtilis, S. lutea and S. aureus is more than 2-aminophenol.
The monomeric, four-coordinate compound, [CoL2] (here LH = Schiff base
obtained from the condensation of cinnamaldehyde and 2-aminophenol) has been
synthesized by refluxing an EtOH solution of Co(OAc)24H2O and LH in 1:2 molar
ratio[54]. LH acts as a monobasic bidentate ON donor ligand. The magnetic moment of the
compound is 5.50 B.M. A tetrahedral structure has been assigned to it.
The blue, six-coordinate compound, [Co(LH)2(H2O)2] (83; M = Co, Y = O, COO)
has been synthesized[55] by refluxing a MeOH solution of LH2 [here LH2 = Schiff base
obtained from the condensation of 1,2,3,5,6,7,8,8a-octahydro-3-oxo-N-1-diphenyl-5(phenylmethylene)-2-naphthalenecarboxamide and 2-aminophenol/2-aminobenzoic acid]
and Co(OAc)24H2O in 1:2 molar ratio for 2 h followed by adjusting the pH to 7.0 using
3% NaOH solution. It is soluble in DMF and DMSO, partially soluble in MeCN and
CHCl3 but insoluble in H2O. The complete loss of coordinated water molecules occurs at
130 oC. The IR data are indicative of the monobasic bidentate ON donor behaviour of the
Schiff base. The carboxylato group is coordinated in a monodentate fashion. The
compound (when Y = O) shows two intense bands one at 13900 cm-1 and another at 18800
cm-1 due to the 4T1g(F) 4A2g(F)(2) and 4T1g(F) 4T1g(P) transitions in an octahedral
environment. These bands occur at 14100 and 18900 cm-1 in the compound (when Y =
COO) respectively. Their magnetic moments (4.86 and 3.18 B.M., when Y = O, COO
22
respectively) indicate a high-spin octahedral environment around Co(II) ion. A transoctahedral structure (83; M = Co, Y = O, COO) has been suggested for them.
A light-brown, four-coordinate, polystyrene-anchored coordination compound,
[PSCH2L(OAc)Co(DMF)] (here PSCH2LH = 68) has been synthesized by refluxing
Co(OAc)24H2O and PSCH2LH in 2:1 molar ratio in N2 atmosphere[25]. The PRC of the
compound is 34.6. The MBC of the ligand is 0.53 mmol of metal per g of it. The
coordinated DMF molecules are coordinated to the metal ion through O atom. The acetato
ligand is coordinated in a monodentate fashion. The Schiff base acts as a monobasic
bidentate ON donor ligand. The magnetic moment (2.40 B.M.) of the compound suggests
a square-planar geometry around the metal ion.
A four-coordinate, non-electrolyte, [Co2(OH)(Cl)(LH)2]H2O (where LH2 = 32) has
been synthesized[8] by mixing CoCl26H2O and LH2 in the presence of Et3N. The ligand
coordinates in a monobasic bidentate ON donor fashion. The magnetic moment of the
compound is 3.4 B.M. A tetrahedral structure has been assigned to it.
A violet, six-coordinate, non-electrolyte (M = 10.6 mho cm2 mol-1 in DMSO),
[CoCl2(LH2)2] (here LH2 = 84; R = 4-OH, R' = Me) is obtained by refluxing
an
H2O/EtOH solution of CoCl26H2O and LH2 in 1:1 molar ratio for 8 h[56]. It is insoluble in
Me2CO, CHCl3 and C6H6 but is fairly soluble in DMF and DMSO. It decomposes between
245-247 oC. LH2 acts as a neutral bidentate ON donor ligand. The coordination compound
displays two bands one at 16338 cm-1 and other at 19330 cm-1 due to the 4T1g(F)
4
A2g(F)(2) and 4T1g(F) 4T1g(P)(3) transitions. The spectral parameters [10Dq (8602 cm-
), B' (860 cm-1), (0.88), 0 (11.4), LFSE (81.9 kJ mol-1)] and the magnetic moment
(5.16 B.M.) support its octahedral geometry. The latter shows higher antibacterial activity
against E. coli than LH2, whereas its antifungal activity against A. niger is less than LH2.
An octahedral structure (85, M = Co) has been assigned to the compound.
Although, LH2 (86) is potentially a dibasic pentadentate O2N3 ligand, it acts as a
monobasic
bidentate
ligand[57]
in
the
brown,
six-coordinate
compound,
[Co(OAc)(LH)(H2O)2]. The bonding takes place through the enolic O and the azomethine
N atoms. The acetato group is coordinated in a bidentate fashion. The OH and NH2 groups
do not participate in the coordination. The magnetic moment (4.71 B.M.) and the
appearance of two bands (17360 and 20964 cm-1) suggest its high-spin octahedral
23
geometry. The ligand has been used for the micro-determination of Co(II) ion within metal
concentration up to 46.3 ppm.
An EtOH solution of Co(OAc)24H2O and LH2 (30, R = H) in 1:2 molar ratio upon
refluxing in the presence of TEM produce[6] a brown-red compound, [Co(LH)2]. It is nonelectrolyte (M = 16 mho cm2 mol-1) and decomposes at 268 oC. LH2 acts as a monobasic
bidentate ON donor ligand.
An EtOH solution of LH2 (87; R = H, 5,6-benzo) reacts with a warmed EtOH
solution of CoCl26H2O in 1:1 molar ratio at pH ~7 and forms[58] the six-coordinate, nonelectrolyte, dinuclear compound, [Co2L2(H2O)4]. It is pink (when R = H) and red (when R
= 5,6-benzo). They are amorphous in nature, having high melting points and are feebly
soluble in DMF and dioxane. The IR data are indicative of the monobasic bidentate ON
donor nature of the ligand per metal ion coordinating through its phenolic O and
azomethine N atoms. The as(O==S==O) and the s(O==S==O) stretches of LH2 occurring
at 1150-1155 and 1320-1330 cm-1 respectively remain at the same energy in the
coordination compounds indicating the non-involvement of sulphone O atom(s) towards
coordination. The (CoO) and the (CoN) vibrations occur at 500, 355 and 505, 350
cm-1 (when R = H, 5,6-benzo respectively). They display the absorption bands at ~8955,
~18125, ~20800 and 32500 cm-1 due to the 4T1g(F) 4T2g(F)(1), 4T1g(F) 4A2g(F)(2),
4
T1g(F) 4T1g(P)(3) and charge transfer transitions respectively indicating the octahedral
environment around the metal ion. The spectral parameters: [10Dq (9170, 8775 cm-1), B'
(809.3, 795.1 cm-1), 2/1 (2.02. 2.00), (0.883, 0.81) and (20.48, 23.45)] further lend
support for their octahedral geometry. Their sub-normal magnetic moments (2.7 and 2.6
B.M.) indicate MM interactions in a polymeric structure. The unpaired electron of the
d-orbital of the metal ion overlaps with the -orbital of the N atom of the azomethine
moiety of the ligands. Due to the high electron density of the N atoms, an electron from N
moves to partially occupied d-orbital of the metal ion with antiparallel spin to the original
d-electron. Thus, the magnetic moments are aligned antiparallel and are responsible for
partial quenching of paramagnetism due to the super-exchange phenomenon. A dinuclear,
octahedral structure (88, R = H, 5,6-benzo; M = Co, A = H2O) has been suggested to it.
Chohan et al.[59] have observed that on refluxing an EtOH solution of CoCl26H2O
and an H2O/EtOH solution of cloxacillin (NaLH, 89) in 1:1 and 1:2 molar ratios, air and
24
moisture-stable,
intense-coloured,
amorphous,
six-coordinate
compounds,
[CoCl(LH)(H2O)3] and [Co(LH)2(H2O)2] respectively are obtained. They are insoluble in

common organic solvents and soluble in H2O, DMF and DMSO. NaLH behaves as a
monobasic bidentate ON donor (carboxylic O and endocyclic N of -lactam ring) ligand.
The carboxylato group is coordinated in a monodentate mode. The presence of the (Co
O) stretch at 525 cm-1 and (CoN) stretch at 410 cm-1 indicates the bonding through O
and N atoms. The presence of the (CoCl) stretch in the former at 320 cm-1 supports the
presence of coordinated chloro group to the metal ion. The former shows the 4T1g(F)
4
T2g(F), 4T1g(F) 4A2g(F) and 4T1g(F) 4T2g(P) transitions at 7375, 17280 and 20595 cm-
and the latter at 7225, 17165 and 20380 cm-1 respectively, for octahedral configuration.
They show antibacterial activities against E. coli, K. pneumoniae, P.
mirabilis, P.
aeruginosa, S. typhi, S. dysentriae, B. cereus, C. diphtheriae, S. pyogenes and S. aureous.

The structures, 90 (M = Co) for [CoCl(LH)(H2O)3] and 91 (M = Co) for [Co(LH)2(H2O)2]
have been assigned.
Amirnasr et al.[60] have synthesized a four-coordinate compound, [CoX2L] [here L
= N,N'-bis(-phenylcinnamaldehyde)-1,2-diaminoethane, X = Cl, Br] by refluxing
CoX26H2O and L in CH2Cl2 in 1:1 molar ratio under N2 atmosphere. It has a distorted
tetrahedral structure.
Upon refluxing an EtOH solution of CoCl26H2O and LH2 (92) in 1:2 molar ratio
for 1 h at pH = 6, a six-coordinate compound, [Co(LH)2(H2O)2] is obtained[61]. It is soluble
in common organic solvents. It is non-electrolyte (M = 11.5 mho cm2 mol-1) in Me2CO.
The (CoN) vibrations occur at 440 cm-1. The Schiff base acts as a bidentate NN donor
ligand. The appearance of two spin-allowed transitions at 17856 and 21734 cm-1 due to the
4
T1g(F) 4A2g(F) and 4T1g(F) 4T1g(P) transitions respectively and the value of magnetic
moment (4.81 B.M.) suggest the high-spin, distorted octahedral geometry around the metal
ion.
The synthesis of a bluish-green, six-coordinate, non-electrolyte, [Co(LH)2(H2O)2]
(83; M = Co, Y = S) has been reported[55]. It is soluble in DMF and DMSO, partially
soluble in MeCN and CHCl3 but insoluble in H2O. The complete loss of the coordinated
H2O molecules occurs at 130 oC. The IR data are indicative of the monobasic bidentate NS
donor behaviour of the Schiff base. The appearance of two intense bands (14000 and
25
19000 cm-1) due to the 4T1g(F) 4A2g(F)(2) and
T1g(F)
T1g(P) transitions
respectively and the magnetic moment (4.90 B.M.) suggest an octahedral environment
B.

Sallam et al.[62] have reported the synthesis of a yellow coordination compound,
[Co(LH)2]2H2O [where LH2 = 93; R' = R'' = Ph, A = (CH2)2] and two brown compounds,
[Co(L'H)2]H2O [here L'H2 = 93; R' = Ph, R'' = Me, A = (CH2)2] and [Co(L''H)(OH)] [here
L''H2 = 93; R' = R'' = Me, A = (CH2)2]. They are insoluble in EtOH, Me2CO, C6H6, CHCl3
and partially soluble in DMF and DMSO. They are non-electrolytes (M = 7.7-9.0 mho
cm2 mol-1) in DMSO. The IR data are indicative of the monobasic tridentate ONO donor
behaviour of these Schiff bases. The (CoO) and the (CoN) vibrations occur
between 519-659 cm-1 and 394-565 cm-1. The octahedral compounds, [Co(LH)2]2H2O and
[Co(L'H)2]H2O exhibit three bands at 17667, 19880 and 22222; 18587, 20833 and 23752
cm-1 due to the 4T1g(F) 4A2g(F) and 4T1g(F) 4T1g(P) and intra-ligand transitions
respectively. The appearance of a band at 18691 cm-1 due to the 4A2 4T2(F) transition in
[Co(L''H)(OH)]
suggests
its
tetrahedral structure.
The
magnetic
moments of
[Co(LH)2]2H2O and [Co(L'H)2]H2O are 5.3 and 5.2 B.M. respectively indicating the
presence of high-spin six-coordinate geometry around the metal ion. The magnetic
moment (3.2 B.M.) of [Co(L''H)(OH)] is intermediate between the values for tetrahedral
and square-planar structures and results from a spin-equilibrium between low- and highspin states. [Co(L'H)2]H2O has an endothermic peak between 46-130 oC indicating the
loss of lattice water molecule. The existence of two exothermic peaks between 156-260
and 370-480 oC indicates the loss of side chain and ligand moieties respectively. CoO is
the final product formed.
A
brown,
monomeric,
six-coordinate,
coordination
compound, [PSLCo(DMF)3] (where PSLH2 = 31) is obtained by refluxing a DMF

swollen suspension of PSLH2 and Co(OAc)24H2O in 1:2 molar ratio for 8 h[7]. The PRC
of the compound is 68.5. The MBC of the ligand is 0.53 mmol of metal per g of it. The
Schiff base acts as a dibasic tridentate ONO donor ligand. DMF molecules are coordinated
to the metal ion. The magnetic moment (4.80 B.M.) and the appearance of three bands at
8300, 12500 and 17860 cm-1 due to the 4T1g 4T2g(1), 4T1g 4A2g(2) and 4T1g(F)
26
4
T1g(P)(3) spin-allowed transitions respectively suggest an octahedral environment around
the metal ion.

Sallam et al.[62] have also reported the syntheses of two brown, four-coordinate
compounds, [Co(OH)(LH)] (where LH2 = 93; R' = R'' = Ph, A = 1,2-C6H4) and
[Co(OH)(L'H)] (here L'H2 = 93; R' = CF3, R'' = thienyl, A = 1,2-C6H4). They are nonelectrolytes (M = 7.3-9.6 mho cm2 mol-1) in DMSO. The IR data are indicative of the
monobasic tridentate ONO donor behaviour of these Schiff bases. The (C==S) stretch
(1264 cm-1) of L'H2 remains at the same energy in [Co(OH)(L'H)] indicating the noncoordinating behaviour of S atom of thienyl moiety. The (CoO) and the (CoN)
vibrations occur between 647-687 cm-1 and 536-580 cm-1. The appearance of two bands at
12269, 16000 and 11111, 16313 cm-1 due to the 2B2g 2Eg and 2B2g 2Ag in
[Co(OH)(LH)] and [Co(OH)(L'H)] respectively is indicative of their square-planar
geometry. The magnetic moments of [Co(OH)(LH)] and [Co(OH)(L'H)] are 1.74 and 1.89
B.M. respectively indicating a low-spin square-planar geometry around the metal ion.
Emara et al.[41] have synthesized a yellowish-blue, four-coordinate compound,
[Co2L(MeOH)2]2MeOH (where LH4 = 70, X = OH) by refluxing a MeOH solution of
LH4 and Co(NO3)26H2O in 1:2 molar ratio for 3 h. It is soluble in common organic
solvents but partially soluble in DMF and DMSO. The (C==N)(azomethine) stretch of
the ligand occurring at 1642 cm-1 shifts to lower energy by 12 cm-1 in the compound. The
IR data are indicative of bis(dibasic tridentate) ONO donor nature of LH4. The (CoO)
and the (CoN) vibrations occur at 608 and 524 cm-1 respectively. The magnetic
moment (4.41 B.M.) and the appearance of three bands at 21834, 20450 and 16420 cm-1
due to the 4A2(F) 4T2(F), 4A2(F) 4T1(F) and 4A2(F) 4T1(P) transitions in the
compound suggest the tetrahedral environment around the metal ion. Both the
uncoordinated and coordinated MeOH molecules are lost by heating the coordination
compound between 35-85 and 85-127 oC respectively.
Tuncel et al.[63] have synthesized a brown, four-coordinate compound, [CoL(H2O)]
(where Na2LH2 = 94, R = H) and another black, four-coordinate compound, [CoL'(H2O)]
(here Na2L'H2 = 94, R = 3-OMe) by refluxing an EtOH solution of CoCl26H2O and an
aqueous solution of LH2 or L'H2 respectively in 1:1 molar ratio. They are soluble in DMF,
DMSO. They are non-electrolytes (M = 15.3 and 13.3 mho cm2 mol-1) in aqueous
27
solution and melt at 203 and 245 oC respectively. The IR data indicate a dibasic tridentate
ONO donor behaviour of the ligands. Their magnetic moments (3.8 and 3.3 B.M.
respectively) indicate a tetrahedral environment around the metal ion. [CoL(H2O)] remains
stable up to 130 oC. The loss of coordinated H2O molecule and the decomposition of
organic skeleton occur between 130-190 oC and 341-585 oC respectively. In case of
[CoL'(H2O)], the above phenomena occurs between 120-185
C and 338-557
respectively. In both the cases, Co3O4 is the final product.

The synthesis of a four-coordinate, high-spin compound, [Co(LH3)(H2O)]nH2O
(where LH5 = 95; R = H, Cl) has been reported[64]. Although the Schiff base is potentially
a pentabasic heptadentate ligand, but acts as a dibasic tridentate ONO donor ligand. A
tetrahedral structure has been suggested for the coordination compound.
An EtOH solution of CoCl26H2O and LH2 [96; R = 3-OMe, R' = OH, R'' = H, R'''
= Me] on stirring forms[65] a light-brown, non-electrolyte, air-stable, four-coordinate
compound, [CoL(H2O)]. The Schiff base coordinates through its phenolic O, azomethine
N and carboxylato O atoms. The band at 16103 cm-1 due to the 4A2 4T1(F) transition
indicates a tetrahedral environment around the metal ion. The compound shows the
ferromagnetic behavior.
The syntheses of a dark-brown compound, [Co(NO3)(LH)(H2O)2]2H2O and
another violet compound, [Co2(OAc)2L(H2O)]2H2O (where LH2 = 32) have been
reported[8]. Both the coordination compounds are non-electrolytes. The ligand is
coordinated in a monobasic tridentate ONO donor fashion. The nitrato group is
coordinated as a monodentate mode in the dark-brown compound, whereas, the acetato
group is coordinated as a monodentate mode as well as bridged-bidentate ligand in the
violet compound. The magnetic moments of the dark-brown and the violet compounds are
4.1 and 2.9 B.M. indicating their high-spin octahedral and tetrahedral geometries
respectively. The occurrence of a band at 16667 cm-1 due to the 4T1g(P) 4A2g transition
in the former and the appearance of two bands one at 18018 cm-1 and other at 15385 cm-1
due to the 4T1g(F) 4A2g(F) and 4T1g 4T2g(F) transitions in the latter also indicate the
same.
Kumar et al.[10] have reported the synthesis of a brown, six-coordinate,
polystyrene-anchored compound, [PSCH2LHCo(DMF)3] (where PSCH2LH3 = 34). The
28
PRC of the compound is 35.4 and the MBC of PSCH2LH3 is 0.22 mmol of Co per g of
due to the 4T1g 4T2g(1), 4T1g 4A2g(2) and 4T1g(F) 4T1g(P)(3) spin-allowed
transitions respectively are indicative of an octahedral environment around the metal ion.
A brown, six-coordinate, binuclear compound, [Co2L2(H2O)4] [where LH2 = 35A35C] is obtained by stirring an EtOH solution of Co(OAc)24H2O and LH2 in 1:2 molar
ratio for 12 h[11]. It melts at 150 oC. It is soluble in most common solvents except ether.
The ligand acts as a dibasic tridentate OON donor ligand. An octahedral geometry [36; M
= Co, A = H2O] has been suggested for it.
The
air-stable,
non-hygroscopic,
non-electrolyte,
dimeric,
six-coordinate
compounds, [CoClL(H2O)]2 (here LH = 43; R = Me, Et, propyl) and [CoCl(L'H)(H2O)]2

(here L'H2 = 43; R = CH2CH2OH) have been synthesized by refluxing a MeOH solution
of CoCl26H2O and LH or L'H2 in 1:1 molar ratio for 4 h[16]. They are soluble in DMF and
DMSO. The coordinated water molecules are lost between 190-200 oC. Although L'H2 is
potentially a dibasic tetradentate NONO donor ligand but similar to LH, it also behaves as
a monobasic tridentate NON donor ligand bridging through its enolic O atom. The
coordination compounds display three bands between 10952-10989, 16806-16949 and
23584 cm-1 due to the 4T1g(F) 4T2g(F)(1), 4T1g(F) 4A2g(F)(2) and 4T1g(F)
4
T1g(P)(3) transitions respectively indicating the octahedral environment around the metal
ion. The magnetic moment (4.54-4.70 B.M.) support the weak anti-ferromagnetic spinexchange interaction between the two Co(II) ions. They exhibit higher antifungal activity
against A. niger than the corresponding ligands. A distorted octahedral structure (44; M =
Co) has been suggested for them.
A violet, nano-crystalline, four-coordinate compound, [CoL(H2O)]Cl (where LH =
97) has been synthesized by refluxing a MeOH solution of CoCl2xH2O and LH in 1:1
molar ratio for 2 h[66]. The complex is 1:1 electrolyte (M = 85 mho cm2 mol-1 in MeOH).
It is soluble in DMF and DMSO. The ligand behaves as a monobasic tridentate NON
donor coordinating through its azomethine N, carboxylato O and imidazole N atoms. The
magnetic moment (4.21 B.M.) and the existence of a band at 17857 cm-1 due to the 4A2(F)
4T1(P) transition indicate a tetrahedral environment around the metal ion. The loss of
29
coordinated H2O molecule, Cl- ion (as HCl gas) and the organic skeleton occur between
210-230, 250-270 and 400-550 oC respectively. Finally CoO is obtained as residue.
A brown, six-coordinate compound, [CoL2] (here LH = 45) is obtained[17] on
refluxing an hot MeOH solution of Co(NO3)26H2O and LH in 1:2 molar ratio at pH = 7.58.5. The compound is non-electrolyte (M = 15.03 mho cm2 mol-1 in DMSO). LH acts as a
monobasic tridentate ONN donor ligand coordinating through its phenolic O and both
azomethine N atoms. The magnetic moment (4.7 B.M.) and the appearance of three bands
at 10162, 18621 and 25575 cm-1 due to the 4T1g(F) 4T1g(P), 4T1g(F) 4A2g and 4T1g(F)
4T1g transitions respectively indicate the presence of high-spin octahedral environment
around the metal ions. The compound crystallizes in a monoclinic fashion with a = 16.038
, b =4.285 and c = 10.692 . The compound shows low antimicrobial activity against
E. coli than S. aureus, however, it shows moderate antimicrobial activity against E. coli
than S. aureus.
The synthesis of a brown, trinuclear compound, [Co3(NO3)2L2(H2O)2]2H2O (LH2
= 70; X = NH2) has been reported[41]. It is soluble in common organic solvents but
partially soluble in DMF and DMSO. The IR data are indicative of bis(monobasic
tridentate) ONN donor nature of LH2. The appearance of four new bands at 1548, 1384,
1302 and 1058 cm-1 indicates the presence of bidentate nitrato group in the compound. The
(CoO) and the (CoN) vibrations occur at 606 and 542 cm-1 respectively. The
magnetic moment (3.20 B.M.) and the appearance of one band at 18868 cm-1 due to the
4
T1g 4T2g transition suggest the low-spin octahedral environment around the metal ion.
A yellowish, four-coordinate, non-electrolyte, [CoL(H2O)] (where LH = 98) has
been synthesized[67]. It is soluble in DMSO. The monobasic tridentate Schiff base

coordinates through its carboxylate O, azomethine N and amino N atoms. The magnetic
moment of the compound is 4.61 B.M. The appearance of a band at 22026 cm-1 due to the
4
A2 4T1(P) transition indicates the tetrahedral geometry around the metal ion. The
compound crystallizes in a monoclinic fashion.

A purple, six-coordinate, non-electrolyte (M = 9.9 mho cm2 mol-1 in DMSO),
[CoCl2(LH)(H2O)]n (here LH = 84; R = H, R' = Me) has been synthesized by refluxing an
H2O/EtOH solution of CoCl26H2O and LH in 1:1 molar ratio for 1 h[56]. The compound is
insoluble in Me2CO, CHCl3 and C6H6 but is fairly soluble in DMF and DMSO. It melts
30
between 240-242 oC. The coordinated H2O molecule is lost at 130 oC. LH acts as a neutral
tridentate ONN donor ligand. The compound displays two bands one at 16130 cm-1 and
other at 19230 cm-1 due to the 4T1g(F)
A2g(F)(2) and 4T1g(F)
T1g(P)(3) transitions
-1
respectively. The spectral parameters [10Dq (8558 cm ), B' (855 cm-1), (0.88), 0
(11.9%) and LFSE (81.4 kJ mol-1)] and the magnetic moment (4.96 B.M.) lend support
for its octahedral geometry. The compound shows higher antibacterial activity against E.
coli than LH, whereas its antifungal activity against A. niger is less than LH. An
octahedral polymeric structure (99, M = Co) has been assigned to the compound.
The
synthesis
of
green,
monomeric,
[Co(LH)(H2O)]Cl (where LH2 = 86) has been reported
[57]
four-coordinate
compound,
. The ligand is linked through its
enolic O, azomethine N and amino N atoms. The phenolic OH group does not participate
in the coordination. The magnetic moment (4.42 B.M.) and the occurrence of two bands at
14749 and 20921 cm-1 suggest a tetrahedral geometry of the compound.
Sebastian et al.[20] have observed that the complexation of the yellow coloured
Schiff base, (LH2 = 46A, 46B) with Co(II) ion proceeds with the rearrangement of
benzothiazoline ring to form the corresponding brown colored, non-electrolyte,
[CoL(H2O)3]H2O. The Schiff base coordinates in enolic form as dibasic tridentate ONS
donor ligand. The magnetic moment (5.18 B. M.) suggests a high-spin octahedral
geometry for the complex. The lattice water molecule and three coordinated water
molecules are lost between 90-120 oC and 150-200 oC respectively.
A brown, mononuclear, six-coordinate compound, [Co(LH2)(H2O)3] (where LH4 =
100) has been synthesized[42]. The Schiff base behaves as a dibasic tridentate ONS donor
ligand coordinating through its enolic O, azomethine N and thiolato S atoms. The oxime
group does not participate in coordination.
A pink, non-electrolyte, [CoL(H2O)2]2, (where LH2 = 47) has been synthesized[21].
The Schiff base acts as a dibasic tridentate ONS donor ligand. The bands at 8728 and
19200 cm-1 due to the 4T1g 4T2g(F) and 4T1g 4T1g(P) transitions respectively and the
magnetic moment (4.86 B.M.) are indicative of the octahedral environment around the
metal ion. Here two cobalt ions are bridged through phenolic O atoms resulting in a dimer.
An aqueous solution of Co(OAc)24H2O reacts[22] with an EtOH solution of LH2
(48) in 1:2 molar ratio in N2 atmosphere and forms an air-stable, reddish-brown
31
compound, [Co(LH)2]. It decomposes at 186 oC and is soluble in Me2CO, DMF and
DMSO. It is non-electrolyte (M = 12.3 mho cm2 mol-1 in DMSO and 3.1 mho cm2 mol-1
in Me2CO). The Schiff base acts as a monobasic tridentate ONS donor ligand and
coordinates to the metal ion through its hydroxylic O, azomethine N and thiolato S atoms.
The (CoN) vibrations occur at 565 cm-1 in the compound. The magnetic moment (4.9
B.M.), the appearance of a broad band (7700 cm-1) and two shoulders (13500 and 20500
cm-1) due to the 4T1g 4T2g(1), 4T1g 4A2g(2) and 4T1g 4T1g(P)(3) transitions
respectively indicate the presence of high-spin octahedral environment around the metal
ion. A distorted octahedral structure, 49 (M = Co) has been suggested for it.
An air-stable, four-coordinate compound, [CoCl(LH)]3H2O (here LH2 = 37) has
been obtained by stirring a MeOH solution of LH2 and CoCl26H2O in 2:1 ratio at pH 8.0
for 8 h[68]. It is soluble in DMSO and DMF, slightly soluble in MeCN and insoluble in
MeOH and H2O. It behaves as non-electrolyte in DMSO. It shows a mass loss equivalent
to three H2O molecules in the 90-110 oC range, suggesting that these molecules are not
coordinated to the metal ion. The carboxylato group is coordinated in a monodentate
mode. The low value of the magnetic moment (4.1 B.M) of the compound indicates its
distorted tetrahedral geometry.
The synthesis of an air-stable, four-coordinate compound, [CoCl(LH)]2H2O (here
LH2 = 39) has been reported[13]. The compound is soluble in DMSO and DMF and slightly
soluble in MeCN. It exhibits the non-electrolytic behavior in DMSO. NaLH behaves as a
monobasic tridentate OON donor ligand. The carboxylato group is coordinated in a
monodentate fashion. The (CoN) stretch occurs at 450 cm-1. The compound shows a
broad band centered at 25640 cm-1 due to Td symmetry around the metal ion. Its magnetic
moment is 3.8 B.M. The compound shows higher activity than NaLH against P. mirabilis,
K. pneumoniae, S. enteriditis and E. coli, while it remains inactive towards S. aureus and
P. aeruginosa. A tetrahedral structure (40, M = Co) has been assigned to it.
A four-coordinate compound, [CoCl(LH)] (here LH2 = 50; R = OMe, R' =
NH2) has been synthesized by stirring a MeOH solution of NaLH and CoCl2.6H2O in
2:1 molar ratio for 8 h at room temperature[43]. It is air-stable and soluble in DMF and
DMSO and is slightly soluble in MeCN. It is non-electrolyte in DMSO. The carboxylato
group is coordinated in a monodentate fashion. The presence of the (CoS) stretch at
32
300 cm-1 indicates the coordination through S atom of thiophene moiety. LH2 behaves as a
monobasic tridentate OOS donor. The magnetic moment of the compound is 4.2 B.M. The
compound is inactive towards S. aureus, E. faecalis, E. coli and P. mirabilis, while it
shows lesser antibactericidal activity than the ligand against S. sonnei and S. enteritidis. A
distorted tetrahedral structure (51; R = OMe, R' = NH2, A = nil; M = Co) has been
assigned to it.
Suni et al.[69] have noticed that upon refluxing an EtOH solution of
Co(OAc)24H2O, LH (52; R = (C5H4N)2C, R' = NHC6H11, X = S) and KSCN in 1:1:1
molar ratios, a brown, four-coordinate compound, [Co(NCS)L]2H2O is obtained. On the
other hand, on refluxing an EtOH solution of CoCl26H2O and L'H (52; R = (C5H4N)2C, R'
= NHC6H5, X = S) in 1:1 molar ratio, another brown, four-coordinate compound,
[CoClL']2H2O is obtained. Both the ligands behave as the monobasic tridentate NNS
donors. The isothiocyanato group behaves as a monodentate N donor ligand. The magnetic
moments of [Co(NCS)L']2H2O and [CoClL]2H2O (3.23 and 3.52 B.M. respectively) and
their g|| (2.299, 2.282) and g (1.996, 1.994) values support their square-planar geometries.
C.

The synthesis of a blackish-brown complex, [CoL(H2O)2] (here LH2 = 54) has
been reported[26] The ligand behaves as a tetradentate ONNO donor coordinating through
its phenolic O and azomethine N atoms. The polymeric high spin octahedral complex
(4.52 B.M.) displays three bands at 9200, 17200 and 27520 cm-1 due to the 4T1g
4
T2g(1), 4T1g 4A2g(2) and 4T1g(F) 4T1g(P)(3) transitions respectively.

A four-coordinate compound, [CoL] (where LH2 = 55) is obtained by refluxing a
MeOH solution of Co(OAc)24H2O and a CH2Cl2 solution of LH2 in 1:1 molar ratio for 17
h[27]. It is unstable in air. It is readily soluble in DMF, DMSO and CHCl3, sparingly
soluble in MeOH and EtOH and insoluble in non-polar solvents. The IR data are indicative
of the dibasic tetradentate ONNO donor nature of the ligand. The compound shows
magnetic moments of 1.9 B.M. indicating the presence of one unpaired electron.
An EtOH solution of Co(OAc)24H2O and LH2 (101) in 1:1 molar ratio on
refluxing for 3 h forms[70] a non-electrolyte (M = 8.36 mho cm2 mol-1 in DMF), fourcoordinate compound, [CoL]2H2O. It melts and decomposes at 285 and 315
33
respectively. LH2 acts as a dibasic tetradentate ONNO donor ligand. The magnetic
moment of the compound is 2.61 B.M. A square-planar structure has been suggested for it.
On refluxing an EtOH solution of LH2 (26; R = 5,6-benzo, R' = OH, R'' = H, R'''
= 1,2-C6H4 or 1,4-C6H4) and an aquoeus solution of CoCl26H2O under N2 atmosphere for
~3 h, the air-stable, non-hygroscopic, brown, monomeric, non-electrolyte (in DMF), [CoL]
is obtained[71]. The compounds are soluble in DMF and DMSO. LH2 acts as a dibasic
tetradentate ONNO donor ligand. The (CoO) and the (CoN) vibrations occur at 458
and 344 cm-1 respectively (when R''' = 1,2-C6H4), while these occur at 477 and 325 cm-1
respectively (when R''' = 1,4-C6H4). The low value of the magnetic moment (2.35 B.M.)
and the presence of the band at 19605 cm-1 in the compound (when R''' = 1,2-C6H4)
indicate a low-spin square-planar environment around the metal ions. The magnetic
moment of the compound (when R''' = 1,4-C6H4) is 2.88 B.M. A square-planar
mononuclear structure, 102 (M = Co) and another dinuclear structure, 103 (M = Co) have
been suggested for them.
The complexes of unsymmetrical Schiff base ligands have been studied for their
dioxygen uptake[72] and their oxidative catalysis[73]. The credit to synthesize the metal
complex of an unsymmetrical Schiff base, LH2 (104) containing two different aldehydes
condensing with o-phenylenediamine goes to Lashanizadegan[74] and his team.
Mononuclear compound [CoL] is obtained by refluxing a MeOH solution of
Co(OAc)24H2O and LH2 (in CH2Cl2) in 1:1 molar ratio. LH2 behaves as a dibasic
tetradentate (ONNO donor) ligand. The complex exihibits a d-d band at 17000 cm-1 due to
the 1A1g 1B1g transition for square-planar geometry.
Metal complexes incorporating S donor group such as thiosemicarbazone are of
interest because of their resemblance to metalloproteins involved in electron transfer in
biological systems[75].
An EtOH solution of Co(OAc)24H2O and LH2 (105; R = H, Cl, Me)
in equimolar amount on refluxing for 4 h produce non-electrolyte (M = 2.7-9.3 mho cm2
mol-1) four-coordinate complex, [CoL] (R = H, Cl) and another six-coordinate complex
[CoL(H2O)2] (R = Me)[76]. The complex is air-stable, non-hygroscopic and soluble in
DMSO. The ligand coordinates to the metal ion through its carboxylic O, ethereal O,
34
azomethine N and thione S atoms. The complexes exhibit (CS) stretch between 612650 cm-1. The magnetic moments of the complexes lie between 4.30-4.83 B.M.
D.

A yellow-brown, monomeric, five-coordinate, non-electrolyte (M = 6.1 mho cm2
mol-1 in DMSO) compound, [Co(LH3)] (where LH5 =106, R = 3-COOH, R' = H, A = NH)
has been synthesized[77]. It melts at 220 oC. LH5 acts as a dibasic pentadentate ONNNO
donor ligand. The compound displays the 4A2I(F) 4EII(F), 4A2I(F) 4EI(F), 4A2I(F)
4
A2I(P) and 4A2I(F) 4EII(P) transitions at 5500, 12500, 16000 and 20000 cm-1
respectively corresponding to its trigonal-bipyramidal geometry. Its magnetic moment is

4.48 B.M.
A five-coordinate compound, [Co(LH)]2H2O (where Na2LH = 62) has been
synthesized by stirring a MeOH solution of Na2LH and CoCl26H2O in 1:1 molar ratio for
1 h at room temperature[35]. It is air-stable and insoluble in H2O, EtOH, C6H6, Me2CO,
MeCN, Et2O, py, DMF and DMSO suggesting that it is polymeric in nature. The noncoordinated H2O molecules are lost between 80-110 oC. The carboxylato group is
coordinated in a monodentate mode ( = 235 cm-1). The ligand behaves as a dibasic
pentadentate ONOON donor. The magnetic moment of the compound is 4.3 B.M
indicating the presence of five unpaired electrons with S = 5/2 ground state. It shows
higher antibactericidal activity than the ligand against S. aureus, E. coli, S. sonnei, P.
mirabilis, S. enteritis and P. aeruginosa. A five-coordinate structure (63, M = Co) has
been assigned to it.
Chandra et al.[78] have synthesized the monomeric, six-coordinate, 1:1 electrolytes
(M = 98-112 mho cm2 mol-1 in DMSO), [CoX(LH2)]X (here X = NO3, Cl, OAc) and
another monomeric, six-coordinate, non-electrolyte (M = 15 mho cm2 mol-1 in DMSO),
[Co(SO4)(LH2)] (here LH2 = 107). LH2 acts as a neutral pentadentate NNSNN donor
ligand coordinating through its imino N, azomethine N and S atoms. The compounds
display the (CoN) and (CoS) vibrations between 403-464 and 335-347 cm-1
respectively. The nitrato, acetato and sulphato groups are coordinated in a monodentate
manner. The compounds display the 4T1g(F) 4T2g(F)(1), 4T1g(F) 4A2g(F)(2) and
4
T1g(F) 4T1g(P)(3) transitions between 9746-10471, 15247-19493 and 18621-22371
cm-1 respectively corresponding to their tetragonal geometries. The spectral parameters
35
[10Dq (9842-11869 cm-1), B' (532-913 cm-1), (0.48-0.81), LFSE (94.07 to 113.4 kJ
mol-1)] account for their covalent nature. The molecular ion, isotopic peaks and base peaks
appear at m/z = 602, 603 (M+ + 1) and 214 respectively. Their magnetic moments lie in
the range 5.01-5.08 B.M. They show enhanced antifungal activity against A. niger, F.
oxysporum, A. brassicae and antibacterial activity against X. compestris, P. aeruginosa
than LH2.
E.

Relatively little work has been reported on Co(II) coordination compounds with
hexadentate ligands. Pal et al.[79] have synthesized a brown, monomeric, non-electrolyte

(M = 3.2 mho cm2 mol-1 in nitromethane), eight-coordinate, low-spin compound,
[CoL(NH3)2] [here LH2 = 1,2-bis(o-salicylaldiminophenylthio)xylene]. The coordinated
NH3 molecules are lost between 180-190 oC. LH2 acts as a dibasic hexadentate N2S2O2
donor ligand. The diamagnetic, six-coordinate compound, [CoL] obtained after the loss of
two NH3 molecules remains stable upto 250 oC. Its magnetic moment is 2.91 B.M.
Fun et al.[80] have synthesized a monomeric, six-coordinate compound, [CoL] (here
LH2 = 108). LH2 acts as a dibasic hexadentate SNOONS donor ligand. A distorted
octahedral structure [109; M = Co] has been suggested for the compound.
Coordination compounds of nickel (II)

Nickel (Ni), a silvery-white d-block transition metal with golden tinge belongs to
Group 10 and Period IV of the Periodic Table. Its atomic number, atomic weight and
electronic configurations are 28, 58.71 amu and [Ar] 3d84s2 respectively. The most
common oxidation state of nickel is +2. It is present in urease, NiFe-hydrogenases,
superoxide dismutase and glyoxalase. Nickel plays numerous roles in biology of microbes
and other living organisms. The ability of Ni(II) ion to form the coordination compounds
with a wide range of ligands has been reported. These ligands are coordinated to Ni(II) ion
in a monodentate, bidentate, tridentate, tetradentate, pentadentate and hexadentate fashion.
We present here a brief survey of the Chemistry of coordination compounds of Ni(II) ion.
A.

An air-stable, non-hygroscopic, non-electrolyte (in DMF), brown, four-coordinate
compound, [Ni(SO4)L2]2H2O (where L = 110; R = 3-NO2, X = O) is obtained by
36
refluxing a MeOH solution of NiSO46H2O and L in 1:2 molar ratio for 4 h[81]. It
decomposes between 204-210 oC. It is soluble in MeOH, EtOH and DMF. L acts as a
neutral monodentate N donor ligand. The furanyl O atom does not participate in
coordination as evident by the occurrence of the (COC) stretch at the same energy
(1170 cm-1) both in L and the compound. The occurrence of two bands at 17200 and
26700 cm-1 due to the 1A1g 1A2g and 1A1g 1B1g transitions respectively and the
diamagnetism of the latter suggest its square-planar geometry. It exhibits fungistatic
activity against A. niger, A. solani, A. carneus and C. capsici.
B.

A pale-green, six-coordinate compound, [Ni(LH)2(H2O)2]3EtOH (here LH2 =
35A-35C) is obtained by stirring an EtOH solution of Ni(OAc)24H2O and LH2 in 1:2

molar ratio for 4 h[11]. It melts at 140 oC. The IR data are indicative of the monobasic
bidentate ON donor behaviour of the ligand. The band at 13020 cm-1 due to the 3A2g
3
T1g transition and the magnetic moment (3.19 B.M.) indicate an octahedral environment

Raman et al.[51] have noticed that when an EtOH solution of NiCl26H2O and LH
(80) is refluxed for 2 h in 1:2 molar ratio, a four-coordinate compound, [NiL2] is obtained.
It is non-electrolyte in EtOH. LH acts as a monobasic bidentate ON donor ligand. The
compound displays a band at 20000 cm-1 due to the 1A1g 1B1g transition supporting a
square-planar geometry. Its antibacterial activity against S. aureus, B. subtilis, E. coli and
A. niger is higher than LH.
Maurya et al.[2] have synthesized a yellow, monomeric, non-electrolyte (M = 9.9
mho cm2 mol-1) four-coordinate compound, [Ni(OAc)L(H2O)] (where LH = 25, R = 3OMe, R' = OH, R'' = H). It decomposes above 360 oC. It is soluble in DMF and DMSO.
The IR data are indicative of the monobasic bidentate ON donor nature of LH. The acetato
ligand is coordinated to the metal ion in a monodentate fashion ( = 320 cm-1). The (Ni
O) and (NiN) vibrations occur at 510 and 400 cm-1 respectively. The magnetic
moment (3.82 B.M.) and the appearance of two bands at 24038 and 31347 cm-1 indicate a
tetrahedral environment around the metal ion.
A MeOH solution of Ni(OAc)24H2O and LH3 (81; R = OH, R' = H) or L'H4 (81; R
= R' = OH) in 1:2 molar ratio on refluxing for 1 h produce[52] a brown, non-electrolyte (M
37
= 7.0 mho cm2 mol-1), diamagnetic, four-coordinate compound, [Ni(LH2)2]H2O or a
greenish-brown, non-electrolyte (M = 4.0 mho cm2 mol-1), diamagnetic, fourcoordinat e, [Ni(L'H3)2]3H2O respectively. They are soluble in DMF, DMSO and THF.
The former melts at 280 oC, while the latter at >300 oC. Both the Schiff bases act as
monobasic bidentate ON donor ligands. The (NiO) and the (NiN) vibrations occur
at 510 and 430 cm-1 in [Ni(LH2)2]H2O and at 495 and 425 cm-1 in [Ni(L'H3)2]3H2O
respectively. The adsorbed H2O molecules from [Ni(LH2)2] H2O and [Ni(L'H3)2]3H2O
are lost between 50-60 oC and 45-60 oC respectively. The endothermic peaks at 280 oC
and 324 oC respectively correspond to their melting points.
Vyas et al.[82] have observed that an aquous solution of Ni(OAc)2 4H2O and an
EtOH solution of LH (111; R = R' = H; R = Me, R' = Cl) on refluxing in equimolar ratio
produce the light-green, non-electrolyte (M = 9.0-11.0 mho cm2 mol-1) compound,
[NiL2(H2O)2]. LH behaves as a monobasic bidentate ON donor ligand. The loss of both
H2O molecules occurs between 161-172 and 170-180 oC respectively (when R = R' = H; R
= Me R' = Cl). The appearance of two bands between 1111-25000 cm-1 are due to the
3
A2g(F) 3T2g(F)(1) and 3A2g(F) 3T1g(F)(2) transitions respectively suggesting an
octahedral geometry around the metal ion in both compounds.

Desai et al.[83] have synthesized the diamagnetic, non-electrolyte heterochelates,
[Ni(LH)L'] (112; R = H, R' = H, Cl, NO2; R = Cl, R' = H; R = Br, R' = H; R = NO2, R' =
H, Cl, MeO; R = Me, R' = H; R = MeO, R' = H; R = EtO, R' = H, M = Ni). The
heterochelates are soluble in glacial AcOH. The IR data are indicative of the monobasic
bidentate ON donor nature of LH2 and the monobasic bidentate OO donor nature of L'H.
A blue, six-coordinate compound, [Ni(LH)2(H2O)2] (83; M = Ni, Y = O, COO) has
been synthesized[55]. It is soluble in DMF and DMSO, partially soluble in MeCN and
CHCl3. The complete loss of water molecules occurs at 130 oC. The Schiff bases act as the
monobasic bidentate ON donor ligands. The carboxylato group is coordinated in a
monodentate fashion. The compounds show intense bands at ~9700, ~16100 and ~24300
cm-1 due to the 3A2g(F) 3T2g(F)(1), 3A2g(F) 3T1g(F)(2) and 3A2g(F) 3T1g(P)(3)
transitions respectively in an octahedral environment. Their magnetic moments are 2.94
and 3.18 B.M. respectively. A trans-octahedral structure (83; M = Ni, Y = O, COO) has
been suggested for them.
38
The synthesis of the dinuclear, non-electrolyte, six-coordinate compound,
[Ni2L2(H2O)4] (where LH2 = 87; R = H, 5,6-benzo) has been reported[58]. It is green (when
R = H) and brown (when R = 5,6-benzo). They are amorphous in nature, having high
melting points and are feebly soluble in DMF and dioxane. The Schiff base coordinates as
a monobasic bidentate (phenolic O and azomethine N atoms) ligand per metal ion. The
sulphone O atom(s) are not involved in coordination as evident from the occurrence of the
as(O==S==O) and the s(O==S==O) stretches at the same energy (1150-1155 and 13201330 cm-1) in LH2 and the compounds. The (NiO) and the (NiN) vibrations occur
at 510, 350 and 500, 340 cm-1 respectively. They exhibit three bands at ~11270, 18360 and
26540 cm-1 due to the 3A2g(F) 3T2g(F)(1), 3A2g(F) 3T1g(F)(2) and 3A2g(F)
3
T1g(P)(3) transitions respectively, indicating their octahedral geometries. The spectral
parameters [10 Dq (11270, 11150 cm-1), B' (739.3, 737.6 cm-1), 2/1 (1.62, 1.63) and
(0.71, 0.70)] also support their octahedral geometries. Their sub-normal magnetic
moments (2.84 and 2.52 B.M.) indicate MM interactions in a polymeric structure. A
dinuclear, octahedral structure (88; M = Ni, A = H2O, R = H, 5,6-benzo) has been
suggested to them.
A green, non-electrolyte (M = 21.2 mho cm2 mol-1 in DMSO), six-coordinate
compound, [NiCl2(LH2)2] (here LH2 = 84, R = 4-OH, R' = Me) has been synthesized by
refluxing an H2O/EtOH solution of NiCl26H2O and LH2 in 1:1 molar ratio for 8 h[56]. It is
insoluble in Me2CO, CHCl3 and C6H6 but is fairly soluble in DMF and DMSO. It
decomposes between 200-202 oC. LH2 acts as a neutral bidentate ON donor ligand. The
compound displays three bands at 8005, 14285 and 24038 cm-1 due to the 3A2g(F)
3
T2g(F) (1), 3A2g(F) 3T1g(F)(2) and 3A2g(F) 3T1g(P) transitions. The spectral
parameters [2/1 (1.62), 10Dq (8805 cm-1), B' (794 cm-1), (0.77), 0 (22.7) and LFSE
(125.7 kJ mol-1)] and the magnetic moment (3.10 B.M.) support an octahedral geometry.
The compound shows higher antibacterial activity against E. coli than LH, whereas its
antifungal activity against A. niger is less than LH. An octahedral structure (85, M = Ni)
has been assigned to it.
An EtOH solution of Ni(NO3)26H2O and LH2 (30, R = H) in 1:2 molar ratio upon
refluxing in the presence of TEM produce[6] a brown-red coordination compound,
39
[Ni(LH)2]. It decomposes at 269 oC. Its molar conductance is 31 mho cm2 mol-1. LH2 acts
as a monobasic bidentate ON donor ligand.
Upon refluxing an EtOH solution of NiCl26H2O and LH2 (92) in 1:2 molar ratio
for 1 h at pH = 6, a six-coordinate, non-electrolyte (M = 11.2 mho cm2 mol-1 in Me2CO)
compound, [Ni(LH)2(H2O)2] is obtained[61]. The Schiff base acts as a monobasic bidentate
NN donor ligand. The (NiN) vibrations occur at 440 cm-1. The appearance of a band at
19240 cm-1 due to the 3A2g(F) 3T1g(P) transition and the value of the magnetic moment
(2.8 B.M.) favour a spin-free octahedral geometry around the metal ion.
The synthesis of a bluish-green, six-coordinate compound, [Ni(LH)2(H2O)2] [83;
M = Ni, Y = S) has been reported[55]. It is soluble in DMF and DMSO, partially soluble in
MeCN and CHCl3. The complete loss of water molecules occurs at 130 oC. The IR data
are indicative of the monobasic bidentate NS donor behaviour of the Schiff base. The
compound shows intense bands at 9800, 16200 and 24300 cm-1 due to the 3A2g(F)
3
T2g(F)(1), 3A2g(F) 3T1g(F)(2) and 3A2g(F) 3T1g(P)(3) transitions respectively in an
octahedral environment. Its magnetic moment is 2.92 B.M.

A brown, four-coordinate, non-electrolyte (M = 0.96 mho cm2 mol-1 in DMF),
[NiL2] (here LH = 52; R = (4-NO2)C6H4C(Me), R' = NHMe, X = S) has been synthesized
by refluxing an EtOH solution of Ni(OAc)24H2O and L in 1:2 molar ratio[84]. LH behaves
as a monobasic bidentate NS donor ligand.
A four-coordinate compound, [NiL2] (here LH = 52; R = C6H13CH, C9H19CH,
C10H21CH; R' = NH2, NHMe, NHCH2CHCH2, X = S) is obtained by stirring an EtOH
solution of Ni(OAc)24H2O and LH in 1:2 molar ratio for 2 h[85]. LH behaves as a
monobasic bidentate NS donor ligand.
A MeOH solution of Ni(OAc)24H2O reacts with an EtOH solution of LH (52; R =
Ph)2C3N2HCH, R' = NH2, X = S) in 1:1 molar ratio and forms[86] a brown, non-electrolyte,
diamagnetic, four-coordinate compound, [NiL2]. It is soluble in DMF. LH acts as a
monobasic bidentate NS donor ligand. The compound crystallizes in a triclinic fashion. Its
crystal parameters are: a = 12.364 , b = 12.451 , c = 12.478 ; = 103.27o, = 92.86o,
= 115.59o and Z = 2. The NNiN angle is deviated from 90o to 102.5o which
indicates the deviation from regular square-planar geometry.
40
C.

Sallam et al.[62] have synthesized six-coordinate compounds, [Ni(LH)2]2H2O
[where LH2 = 93; R' = R'' = Ph, A = (CH2)2, 1,2-C6H4], four-coordinate, [Ni(L'H)(OH)]
[here L'H2 = 93; R' = R'' = Me, A = (CH2)2, 1,2-C6H4], [Ni(L''H)(OH)]xH2O [here L''H2 =
93; R' = Ph, R'' = Me, A = (CH2)2, x =1), 93; R' = CF3, R'' = thienyl, A = 1,2-C6H4, x = 2].
They are non-electrolytes (M = 0.5-25.0 mho cm2 mol-1) in DMSO. The IR data are
indicative of the monobasic tridentate ONO donor behaviour of the ligands. The (NiO)
and the (NiN) vibrations occur between 521-676 cm-1 and 410-588 cm-1 respectively.
[Ni(LH)2]2H2O adopts an octahedral structure as evident by the appearance of two bands
at 15384, 16558 and 20000, 18484 cm-1 due to the
A2g 3T1g(F) and 3A2g 3T1g(P)
transitions respectively. [Ni(L''H)(OH)]xH2O (here x = 1) and [Ni(L'H)(OH)] (when A =

1,2-C6H4) adopt a square-planar geometry. On the other hand, [Ni(L''H)(OH)] [when A =
(CH2)2] and Ni(L''H)(OH)]xH2O (here x = 2) possess the tetrahedral and pseudotetrahedral environments respectively around the metal ions. Their magnetic moments lie
between 1.7-3.7 B.M. [Ni(L''H)(OH)]H2O shows an endothermic peak between 40-113 oC
indicating the loss of lattice water molecule. The existence of two exothermic peaks
between 213-323 and 363-493 oC indicate the loss of one Ph and ligand moieties
respectively. NiO is the final product formed.
The syntheses of a black, four-coordinate compound, [NiL(H2O)]H2O (where
Na2LH2 = 94, R = H) and another brown, four-coordinate, [NiL'(H2O)]H2O (here Na2L'H2
= 94, R = 3-OMe) have been reported[63]. They are non-electrolytes (M = 17.9 and 14.1
mho cm2 mol-1) in aqueous solution. They melt at 220 and 258 oC respectively. The IR
data indicate a dibasic tridentate ONO donor behaviour of the ligands. The magnetic
moments of both the compounds are 2.2 B.M. indicating a tetrahedral environment around
the metal ions. [NiL(H2O)]H2O is stable up to 60 oC. The loss of non-coordinated and
coordinated H2O molecules takes place between 60-95 oC and 135-210 oC respectively.
The decomposition of organic skeleton occurs between 355-560 oC and finally NiO is
obtained. In case of [NiL'(H2O)]H2O, the loss of non-coordinated and coordinated H2O
molecules takes place between 65-110 oC and 130-190 oC respectively. Here, the
decomposition of organic skeleton occurs between 359-585 oC and finally NiO is
obtained.
41
Emara et al.[41] have synthesized a green, six-coordinate, dinuclear compound,
[Ni2L(MeOH)4(H2O)2]MeOH1H2O
(where LH4 = 70, X = OH) by refluxing a
MeOH solution of Ni(NO3)26H2O and LH4 in 2:1 molar ratio for 3 h. It is soluble in
common organic solvents but partially soluble in DMF and DMSO. The (NiO) and the
(NiN) vibrations occur at 590 and 514 cm-1 respectively. The IR data are indicative of
bis(dibasic tridentate) ONO donor nature of LH4. The magnetic moment (3.18 B.M.) and
the appearance of two bands, one at 13928 cm-1 and the other at 19531 cm-1 due to the
3
A2g(F) 3T1g(F) and 3A2g(F) 3T1g(P) transitions suggest the octahedral environment

Kumar et al.[10] have synthesized a green-yellow, polystyrene-anchored sixcoordinate compound, [PSCH2LHNi(DMF)3] (where PSCH2LH3 = 34) by refluxing a
DMF swollen suspension of PSCH2LH3 and a DMF solution of Ni(OAc)2 4H2O. The
PRC of the compound is 90.2 and the MBC of PSCH2LH3 is 0.56 mmol of Ni per g of
due to the 3A2g(F) 3T2g(F)(1), 3A2g(F) 3T1g(F)(2) and 3A2g(F) 3T1g(P)(3)
transitions respectively indicate an octahedral environment around the metal ion.
A yellowish-green, binuclear, six-coordinate compound, [Ni2L2(H2O)4] (here LH2
= 35A-35C) is obtained by stirring an EtOH solution of Ni(OAc)24H2O and LH2 in 1:2
molar ratio in the presence of LiOH for 4 h[11]. It melts at 198 oC. It is soluble in Me2CO
but insoluble in MeOH. The IR data are indicative of the dibasic tridentate OON donor
behaviour of the ligand. The lower value of the magnetic moment (4.44 B.M.) of the
binuclear compound indicates a slight anti-ferromagnetic interactions between the adjacent
Ni(II) ions. An octahedral structure (36; M = Ni, A = H2O) has been suggested for it.
A four-coordinate, non-electrolyte (in DMSO), [NiCl(LH)]3H2O (here LH2 = 39)
has been synthesized by stirring a MeOH solution of NiCl26H2O and NaLH in 1:2 molar
ratio for 8 h at room temperature[13]. It is air-stable, soluble in DMSO and DMF and
slightly soluble in MeCN. NaLH behaves as a monobasic tridentate OON donor. The
carboxylato group is coordinated in a monodentate fashion. The (NiN) stretch occurs at
450 cm-1. The compound shows two bands at 23697 and 12500 cm-1 due to the 3T1(F)
3
T2(F) and 3T1(F) 3A2(F) transitions respectively. Its magnetic moment (3.2 B.M.)
42
indicates the presence of two unpaired electrons. It shows higher activity than the ligand
against S. aureus, P. mirabilis, K. pneumoniae, S. enteriditis and E. coli, while remains
inactive towards P. aeruginosa. A tetrahedral structure (40; M = Ni) has been assigned to
it.
The
air-stable,
non-hygroscopic,
non-electrolyte,
dimeric,
six-coordinate
compounds, [NiClL(H2O)]2 (here LH = 43; R = Me, Et, propyl) and [NiCl(L'H)(H2O)]2

(here L'H2 = 43; R = CH2CH2OH) have been synthesized by refluxing a MeOH solution
of NiCl22H2O and LH or L'H2 in 1:1 molar ratio for 4 h[16]. They are soluble in DMF and
DMSO. The coordinated water molecules are lost between 190-200 oC. Although L'H2 is
potentially a dibasic tetradentate NONO donor ligand but similar to LH, it also behaves as
a monobasic tridentate NON donor ligand bridging through its enolic O atom. The
compounds display three bands at 11273-11363, 16339-16366 and 27700 cm-1 due to the
3
A2g(F)
T2g(F)(1),
A2g(F)
T1g(F)(2) and
A2g(F)
T1g(P)(3) transitions
respectively. The spectral parameters [2/1 (1.43-1.44), 10Dq (11300-11360 cm-1), B'
(669-681 cm-1), (0.65-0.66) and LFSE (32.2 to -32.4 kcal mol-1)] and their magnetic
moments (3.15-3.20 B.M.) support an octahedral geometry. The compounds exhibit higher
antifungal activity against A. niger than the corresponding ligands. A distorted octahedral
structure (44; M = Ni) has been suggested for them.
A pale green, nano-crystalline, four-coordinate complex, [NiL(H2O)]Cl (where LH
= 97) has been synthesized by refluxing a MeOH solution of NiCl2xH2O and LH in 1:1
molar ratio for 2 h[66]. The complex is 1:1 electrolyte (M = 80 mho cm2 mol-1 in MeOH).
It is soluble in DMF and DMSO. The ligand behaves as a monobasic tridentate NON
donor coordinating through its azomethine N, carboxylato O and imidazole N atoms. The
magnetic moment (3.32 B.M.) and the existence of a band at 16393 cm-1 due to the 3T1(F)
3T1(P) transition indicate a tetrahedral environment around the metal ion. The loss of
coordinated H2O molecule, Cl- ion (as HCl gas) and organic skeleton occur between 208227, 252-270 and 410-553 oC respectively. Finally NiO is obtained as residue.
Leovac et al.[87] have claimed to be the first to synthesize a binuclear Ni(II)
coordination compound involving semicarbazone moiety. An aqueous solution of
Ni(NO3)26H2O, in the presence of NaN3, on warming with Schiff base, LH32H2O (113; R
= NHCONH2) in 1:2.5:1 molar ratios forms a mixture of dark-green crystalline, six-
43
coordinate, dimeric compound, [Ni2(LH3)2(1,1-N3)2(N3)2]2H2O as a main product and a
red crystalline, six-coordinate, [Ni(LH2)2]2H2O as admixture. They are air-stable and
fairly soluble in DMF and DMSO. The molar conductances of the dimeric and monomeric
compounds are 30.5 and 7.2 mho cm2 mol-1 in DMSO and DMF respectively. The ligand
acts as a neutral tridentate ONO donor and as a monobasic tridentate ONO donor ligand in
the dimeric and monomeric compounds respectively. The magnetic moment of the dimeric
species is 2.80 B.M. The latter crystallizes in a triclinic fashion with crystal parameters: a
= 8.515 , b = 8.715 , c = 11.031 , = 68.42o, = 81.84o, = 66.00o and Z = 1. The
monomeric species crystallizes in a monoclinic fashion. Its crystal parameters are: a =
16.306 , b = 13.552 , c = 12.487 , = = 90.0o, = 125.11o and Z = 4.
The syntheses of a red, four-coordinate compound, [Ni(NCS)(LH)] and another
deep-red, four-coordinate, crystalline compound, [Ni(N3)(L'H)] (where LH2 = 114; R =
Me, L'H2 = 114; R = Et) have been reported[88]. The (NiO) and (NiN) frequencies
occur at 459 and 360 cm-1 in [Ni(NCS)L], while at 462 and 358 cm-1 in [NiN3L']
respectively. LH2 and L'H2 behave as monobasic tridentate ONN donor ligands. The
isothiocyanato ligand is coordinated to Ni through its N atom as evident by the presence of
a single peak at 2103 cm-1 in [Ni(NCS)(LH)]. The coordinated azide ligand exhibits the
(NNN) stretch at 2021 cm-1 in [Ni(N3)(L'H)]. The bands at 23530 and 30303 cm-1 in
MeCN solution of [Ni(NCS)(LH)] and at 23753 and 31033 cm-1 in [Ni(N3)(L'H)] are due
to the d-d transitions in a square-planar environment. [Ni(NCS)(LH)] remains stable up to
~195 oC and then begins to lose LH2 in two steps between 195-240 and 240-330 oC. The
final decomposition leads to a black residue as NiO. The compounds crystallize in the
monoclinic fashions with central Ni(II) ion displaying a distorted square-planar geometry.
A red, four-coordinate, dinuclear compound, [Ni2L(MeOH)2](NO3)2H2O (where
LH2 = 70; X = NH2) has been synthesized by refluxing a MeOH solution of LH2 and
Ni(NO3)26H2O in 1:2 molar ratio for 3 h[41]. It is soluble in common organic solvents but
partially soluble in DMF and DMSO. The IR data are indicative of bis(monobasic
tridentate) ONN donor nature of LH2. The appearance of two new bands at 1384 and 856
cm-1 in the compound indicates the presence of ionic nitrate group. The (NiO) and the
(NiN) vibrations occur at 596 and 480 cm-1 respectively. The diamagnetic nature of the
44
compound and the appearance of a band at 18182 cm-1 due to the 1A1g 1B1g transition
suggest a square-planar environment around the metal ion.
A green, non-electrolyte (M = 30.3 mho cm2 mol-1 in DMSO), six-coordinate
compound, [NiCl2(LH)(H2O)]n (here LH = 84; R = H, R' = Me) is obtained by refluxing an
H2O/EtOH solution of NiCl26H2O and LH in 1:1 molar ratio for 1 h[56]. It is insoluble
Me2CO, CHCl3 and C6H6 but is fairly soluble in DMF and DMSO. It melts between 195197 oC. LH acts as a neutral tridentate ONN donor ligand. The compound shows three
bands at 10671, 15479 and 25000 cm-1 due to the 3A2g(F) 3T2g(F)(1), 3A2g(F)
3
T1g(F)(2) and 3A2g(F) 3T1g(P) transitions respectively. The spectral parameters (2/1 =
1.46, 10Dq = 10671 cm-1, B' = 750 cm-1, = 0.71, 0 = 28.9, LFSE = 152.4 kJ mol-1) and
the magnetic moment (2.86 B.M.) afford its octahedral geometry. The compound shows
higher antibacterial activity against E. coli than LH, whereas its antifungal activity against
A. niger is less than LH. An octahedral polymeric structure (99; M = Ni) has been
assigned to it.
A MeOH solution of Ni(ClO4)26H2O on stirring with a MeOH solution of LH(here
LH = 115) gives a green colored hexagonal crystals of a mononuclear complex,
[Ni(LH)L](ClO4)0.16H2O[89]. The IR data are indicative of the involvement of phenolic
O, azomethine N and pyridine N atoms of LH towards coordination. The magnetic
moment (2.77 B.M.) and the appearance of intense bands at 40816, 26178 and 15625 cm-1
due to the 3A2g(F) 3T2g(F)(1), 3A2g(F) 3T1g(F)(2) and 3A2g(F) 3T1g(P)(3) spinallowed transitions respectively account for the octahedral environment around the metal
ion. The single crystal X-rays diffraction studies reveal that two tridentate Schiff base
ligands (of which one of the phenolic group is deprotanated) are bonded to the Ni(II),
resulting in a mer octahedral geometry for the non-fluorescent complex. The compound
crystallizes in a monolinic fashion with crystal parameters: a = 31.292 , b = 12.047 , c
= 19.679 , = 90.0o, = 99.7o, = 90.0o and Z = 2.
On refluxing an hot MeOH solution of Ni(NO3)26H2O and LH (45) in 1:2 molar
ratio at pH = 7.5-8.5, a yellow, six-coordinate, non-electrolyte (M = 25.05 mho cm2 mol-1
in DMSO) [NiL2] is obtained[17]. LH acts as a monobasic tridentate ONN donor ligand
coordinating through its phenolic O and both azomethine N atoms. The magnetic moment
(2.92 B.M.) and the appearance of the bands at 12562, 17482 and 25641 cm-1 due to the
45
3
A2g(F) 2T2g, 3A2g(F) 2T1g and 3A2g(F) 2T1g(P) transitions respectively indicate the
presence of octahedral environment around the metal ion. The compound crystallizes in a
monoclinic fashion with a = 10.053 , b = 8.571 and c = 9.830 . It shows low
antimicrobial activity against E. coli than S. aureus.
Choudhary et al.[90] have synthesized a dinuclear coordination compound,
[NiL(H2O)]2 (where LH2 = 116; R = R' = H) by refluxing an H2O/MeOH solution of
NiCl26H2O and a MeOH solution LH2 in 1:1 molar ratio for h in the presence of
AcONa. The synthesis of [NiLA] (where A = py, -, -, -picoline) has also been reported.
The compound and the adducts are air-stable. They are non-electrolytes in DMF. They do
not lose either A or H2O below 90 oC indicating the bonding between A and Ni. The
adducts are fairly soluble in CHCl3, dioxane, C6H6 and DMF, on the other hand,
[NiL(H2O)]2 is insoluble in non-polar solvents like CHCl3, MeOH, EtOH and C6H6
indicating its dimeric or polymeric nature. The IR data indicate the dibasic tridentate ONS
donor nature of the ligand. The presence of py/picoline ring breathing modes at 1008 cm-1
in adducts indicates the coordinated nature of py or picoline molecule. The magnetic
moment of [NiL(H2O)]2 is 1.08 B.M. indicating some distorted Ni(II) species formed by
polymerization of some planar Ni(II) molecules. The diamagnetism of [NiLA] suggests its
four-coordinate, square-planar geometry.
The complexation of the yellow coloured benzothiazoline, LH2 (46A, 46B) with
Ni(II) ion proceeds with the rearrangement of benzothiazoline ring to form the
corresponding red coloured, non-electrolyte, [NiL(H2O)3][20]. The benzothiaoline in the
presence of Ni(II) ion rearranges to form Schiff base. All the three coordinated water
molecules are lost between 150-200 oC. The Schiff base coordinates in enolic form as
dibasic tridentate ONS donor. The magnetic moment (3.27 B. M.) and the presence of
three spin-allowed transitions, 3A2g(F) 2T2g, 3A2g(F) 2T1g and 3A2g(F) 2T1g(P) with
very low intensities suggest an octahedral geometry for the compound.
An aqueous solution of Ni(NO3)26H2O, in the presence of NaN3 on warming with
LH32H2O (113; R = NHCSNH2) in 1:2:1 molar ratios forms[87] a red microcrystalline,
four-coordinate, diamagnetic, square-planar compound, [NiN3(LH2)]H2O. However,
under the same conditions, in the absence of NaN3, a brown crystalline, six-coordinate
compound, [Ni(LH3)2](NO3)2H2O is obtained. The compounds are air-stable. They are
46
sparingly soluble in ROH but fairly soluble in DMF and DMSO. The molar conductances
of [NiN3(LH2)]H2O and [Ni(LH3)2](NO3)2H2O are 7.5 and 202 mho cm2 mol-1) in DMF
and
H2O
respectively.
LH2
acts
as
neutral
tridentate
ONS
donor
in
[Ni(LH3)2](NO3)2H2O and as a monobasic tridentate ONS donor ligand
in
[Ni(LH2)N3]H2O. The appearance of a band at 21277 cm-1 in [Ni(LH3)2](NO3)2H2O

supports its distorted octahedral geometry. [Ni(LH3)2](NO3)2H2O crystallizes in a triclinic
fashion with crystal parameters: a = 10.945 , b = 16.678 , c = 8.101 , = 99o, =
105.89o, = 101.64o and Z = 2.
An aqueous solution of Ni(OAc)24H2O reacts with an EtOH solution of LH2 (48)
in 1:2 molar ratio and forms[22] a yellowish-green, air-stable, six-coordinate, nonelectrolyte (M = 12.8 mho cm2 mol-1 in DMSO and 4.0 mho cm2 mol-1 in Me2CO),
[Ni(LH)2]. It decomposes at 198 oC. It is soluble in Me2CO, DMF and DMSO. The Schiff
base acts as a monobasic tridentate ONS donor ligand coordinating through its alcoholic
O, azomethine N and thiolato S atoms. The (NiN) vibrations occur at 565 cm-1. The
magnetic moment of the compound is 3.1 B.M. An octahedral structure (49; M = Ni) has
been suggested for it.
The syntheses of a green, four-coordinate compound, [NiCl(LH)] and a fivecoordinate heterochelate, [NiClLL'] (here LH2 = 50; R = H, R' = Me, L' = imidazole) have
been reported[23]. The compound and the heterochelate are air-stable, soluble in DMSO
and DMF, slightly soluble in MeCN and insoluble in MeOH and H2O. They are nonelectrolytes in DMSO. The carboxylato group is coordinated in a monodendate mode. The
presence of (NiS) stretch indicates the coordination through thiophene S atom. The
compound shows antibacterial activity higher than the ligand against S. Aureus, E. coli, K.
pneumoniae and S. enteriditis, while it shows lesser activity against P. mirabilis. On the
other hand, the heterochelate shows antibacterial activity higher than the ligand against K.
pneumoniae, lesser activity against S. Aureus, E. coli and P. mirabilis. It remains inactive
against S. enteriditis. A tetrahedral structure (51; R = H, R' = Me, M = Ni, A = nil) and a
trigonal-bipyramidal structure (51; R = H, R' = Me, M = Ni, A = imidazole) have been
assigned to the compound and the heterochelate respectively.
A four-coordinate, non-electrolyte (in DMSO), [NiCl(LH)] (where LH2 = 50; R =
OMe, R' = NH2) has been synthesized by stirring a MeOH solution of NiCl26H2O and
47
NaHL in 1:2 molar ratio for 8 h at room temperature[43]. It is air-stable and soluble in DMF
and DMSO and slightly soluble in MeCN. The energy difference ( = 250 cm-1) between
the as(COO) and s(COO) stretches suggests the monodentate coordinating behaviour of
the carboxylato group. The presence of (NiS) stretch at 300 cm-1 indicates the
coordination through S atom of thiophene moiety. LH2 behaves as a monobasic tridentate
OOS donor ligand. The magnetic moment of the compound is 3.5 B.M. The latter remains
inactive towards E. faecalis and E. coli, while it shows lesser antibactericidal activity than
LH2 against S. aureus, S. sonnei, P. mirabilis and S. enteritidis. A distorted tetrahedral (51;
R = OMe, R' = NH2, M = Ni, A = nil) has been assigned to it.
A six-coordinate compound, [Ni(LH)2]4H2O (where LH2 = penicillin) has been
synthesized by stirring an aqueous solution of sodium penicillinate and NiCl2 in 1:1 ratio
for 1 h at room temperature[91]. LH2 behaves as a monobasic tridentate OOO donor ligand.
The carboxylato group is coordinated in a monodentate mode ( = 224 cm-1). The
compound shows a magnetic moment of 2.86 B.M. An octahedral structure (117, M = Ni,
x = 4) has been assigned to it.
A pale-green, six-coordinate, crystalline compound, [Ni(NO3)2L] (here L = 118) is
obtained by stirring overnight a MeOH solution of L and Ni(NO3)26H2O in 1:1 molar
ratio[92]. The loss of L occurs at 273 oC and those of 2 moles of NO2 and mole of O2 at
482 oC. The Schiff base acts as a neutral tridentate N3 donor ligand. The magnetic moment
of the compound is 3.9 B.M. Its ESR spectral parameters are: gz = 2.16, gx = 2.06, gy =
1.99 and gav = 2.07. The metal ion is coordinated by three N atoms of L with two pyridine
N atoms occupying the trans-positions. L binds to the metal ion by a near-planar fivemembered and a puckered six-membered chelate ring. Out of the two nitrato ligands, one
coordinates in a bidentate fashion, while other adopts a monodentate fashion affording an
overall pseudo-octahedral geometry around the metal ion. The compound crystallizes in a
monoclinic mode with lattice parameters: a = 8.5688 , b = 14.6361 , c = 12.5218 ,
= = 90o, = 97.317o and Z = 4.
The syntheses of a light-brown to dark-brown, six-coordinate compound,
[NiL2]2H2O, heterochelate, [NiLD]yH2O and a dimeric, four-coordinate heterochelate,
[Ni2(SO4)L2]2H2O (here LH = 52; R = (C5H4N)2C, R' = NHPh, X = S, D = NCS, y = 2; D
= Cl, y = 3; D = N3 ; y = 4.5) have been reported[93]. LH acts as a monobasic tridentate
48
NNS donor ligand coordinating through py N, azomethine N and thiolato S atoms. A
distorted octahedral geometry to [NiL2]2H2O and a square-planar geometry to
[NiLD]yH2O and [Ni2 L2(SO4)]2H2O have been assigned.
A MeOH solution of Ni(ClO4)26H2O and LH [52; R = (3-SMe)(5-Me)C4HN2]CH,
R' = SMe, SCH2C6H5, X = S] in 1:2 molar ratio upon refluxing produce[94] a six-coordinate
compound, [NiL(LH)]ClO4. LH acts as a neutral tridentate as well as monobasic tridentate
NNS donor ligand by coordinating through pyrimidyl N, azomethine N and thione or
thiolato S atoms. The compound shows three bands at 12000, 22000 and 26455 cm-1 due
to the 3A2g(F) 3T2g(F)(1), 3A2g(F) 3T1g(F)(2) and 3A2g(F)
o
T1g(P) transitions
respectively. The NNiN (76.06 ), NNiS (80.57 ) and NNiS (108.55o)

angular distortion indicate that the coordination polyhedron is distorted in the compound
due to the steric interaction and asymmetric nature of the ligand, supporting its distorted
octahedral geometry. The ligand field parameters (Dq = 1200 cm-1, B = 831 cm-1 and =
0.78) support an octahedral geometry of the compound.
A brown, six-coordinate, non-electrolyte, [NiL2]2DMSO (where LH = 52; R =
(C9H6N)CH, R' = NH2, X = Se) has been synthesized by stirring an aqueous solution of
Ni(OAc)24H2O and an EtOH solution of LH in 1:1 molar ratio for 1 h[95]. It is soluble in
MeOH, EtOH, MeCN, DMF and DMSO. The IR data indicate a monobasic tridentate
NNSe donor behavior of the ligands. The coordination sites are Se, quinoline N
azomethine N-atoms. The compound crystallizes in a triclinic fashion with lattice
parameters: a = 10.49 , b = 10.89 , c = 15.04 , = 92.3o, = 94.1o and = 116.4o. A
distorted octahedral geometry has been assigned to it.
D.

A reddish-brown, non-electrolyte (M = 10.3 mho cm2 mol-1), six-coordinate
compound, [NiL(H2O)2] (here LH2 = 26; R = 3-OMe, R' = OH, R'' = H, R''' = C2H4) is
obtained by refluxing a mixture of an H2O/EtOH solution of Ni(OAc)24H2O and a DMF
solution of LH2 in 1:1 molar ratio for 4 h[79]. It decomposes at 240 oC. It is soluble in DMF
and DMSO. The Schiff base acts as a dibasic tetradentate ONNO donor ligand. The
compound shows (NiO) and (NiN) vibrations at 520 and 450 cm-1 respectively. Its
magnetic moment is 3.01 B.M. indicating an octahedral environment around the metal ion.
49
Mukherjee et al.[96] have synthesized a green, six-coordinate, monomeric, nonelectrolyte compound, [Ni(NCS)(LH)(H2O)]H2O [LH2 = 26; R = R'' = H, R' = OH, R''' =
(CH2)3]
and
red,
six-coordinate,
non-electrolyte,
trinuclear
heterochelates
[(NiL')2Ni(NCS)2] [L'H2 = 26; R = R'' = H, R' = OH, R''' = (CH2)2CH(Et)] and

[(NiL'')2Ni(NCS)2] [L''H2 = 26; R = R'' = H, R' = OH, R''' = (CH2)2] by refluxing a MeOHH2O (9:1 v/v) solution of Ni(NCS)24H2O and MeOH solution of appropriate ligand in 3:2
molar ratio. The Schiff base acts as a monobasic tetradentate ONNO donor ligand in
[Ni(NCS)(LH)(H2O)]H2O, while in [(NiL')2Ni(NCS)2] and [(NiL'')2Ni(NCS)2] it acts as a
dibasic tetradentate ONNO donor ligand. [Ni(NCS)(LH)(H2O)]H2O loses the coordinated
and lattice water molecules at 150 oC. On dehydration, a dirty-green, five-coordinate
compound, [Ni(NCS)(LH)] with a magnetic moment of 3.0 B.M. is obtained.
[(NiL')2Ni(NCS)2] shows the presence of both square-planar and octahedral Ni(II) ion.
[Ni(NCS)(LH)(H2O)]H2O and [(NiL')2Ni(NCS)2] crystallizes in the monoclinic fashions
The lattice parameters for the former are: a = 10.724 , b = 12.710 , c = 14.875 , =
= 90o, = 104.49o and for the latter: a = 11.384 , b = 20.800 , c = 18.011 , = =
90o, = 103.74o respectively. A distorted octahedral geometry has been assigned to them.
An air-stable, four-coordinate compound, [NiL] (where LH2 = 55) is obtained by
refluxing a MeOH solution of Ni(OAc)24H2O and a CH2Cl2 solution of LH2 in 1:1 molar
ratio for 17 h[27]. It is readily soluble in DMF, DMSO and CHCl3, sparingly soluble in
MeOH and EtOH. The IR data are indicative of the dibasic tetradentate ONNO donor
nature of the ligand.
An EtOH solution of Ni(OAc)24H2O and LH2 (101) in 1:1 molar ratio on
refluxing for 3 h forms[70] a four-coordinate, diamagnetic compound, [NiL]2H2O. The
latter melts and decomposes at 315 and 339 oC respectively. It is non-electrolyte (M =
5.32 mho cm2 mol-1) in DMF. LH2 acts as a dibasic tetradentate ONNO donor ligand. A
square-planar structure has been suggested for the compound.
The synthesis of four coordinate compound, [NiL] (here LH2 = 119; R = H, 5-Cl,
5-NO2, 3-OEt) has been reported[97]. The unsymmetrical tetradentate Schiff base
coordinates through its both phenolic O and the azomethine N atoms. The compounds
show two bands one between 20619-20747 and other between 25773-26178 cm-1 due to
the 1A1g 1B1g and 4A1g 1Eg transitions respectively in square-planar geometry. The
50
thermal studies reveal a single step decomposition pattern due to loss of part of organic
moiety.
Mononuclear, red colored compound [NiL] is obtained by stirring an EtOH
solution of Ni(OAc)24H2O and LH2 (104) in equimolar ratio[74]. LH2 behaves as a dibasic
tetradentate (ONNO donor) ligand. The complex crystallizes in a triclinic fashion with a =
7.9784 , b = 10.2417 , c = 13.4090 , = 103.848o, = 97.05o, = 92.24o and Z = 2.
The diamagnetic complex has a square-planar geometry around the Ni(II) ion.
On refluxing a mixture of an EtOH solution of LH2 (26; R = H, 5,6-benzo, R' =
OH,
R'' = H, R''' = 1,2-C6H4) and an aqueous solution of NiCl26H2O under N2
atmosphere for 3 h, an air-stable, non-hygroscopic, non-electrolyte (in DMF), [NiL] (102,

M = Ni) is obtained[71]. It is red when R = H and is brown when R = 5,6-benzo. On the
other hand, under the similar conditions, a brown, dimeric compound, [NiL']2 (where L'H2
= 26; R = H, 5,6-benzo, R' = OH, R'' = H, R''' = 1,4-C6H4) is obtained. They are soluble in
DMF and DMSO. LH2 and L'H2 act as the dibasic tetradentate ligands. The (NiO) and
the (NiN) vibrations occur between 409-458 and 335-344 cm-1 respectively. The
former two compounds are diamagnetic, suggesting their square-planar geometries. The
magnetic moment of the dimeric compound is 3.57 B.M. (when R = H) and is 3.79 B.M.
(when R = 5,6-benzo). As a result of the higher values of the magnetic moments than the
spin-only value, a tetrahedral, dinuclear structure (103) has been assigned to them.
An EtOH solution of Ni(OAc)24H2O and LH2 (105; R = H, Cl, Me) in 1:1 ratio
on refluxing for 4 h produce an air-stable, non-hygroscopic, non-electrolyte (M = 1.4-2.7
mho cm2 mol-1), [NiL][76]. The latter is soluble in DMSO. The ligand coordinates to the
metal ion through its carboxylic O, ethereal O, azomethine N and thione S atoms. The
compounds exhibit the (CS) stretch between 625-639 cm-1. Their magnetic moments
lie between 3.00-3.19 B.M.
The use of 120 [R = R' = H; R'' = R''' = C6H4(2-OH)] as an ion-exchanger in the
recovery of heavy metals is well known[98]. Beraldo et al.[99] have synthesized the
black/dark-green, four-coordinate, diamagnetic compound, [NiL] (where LH2 = 121; R =
NHMe, NHEt, NMe2, piperidine) by refluxing a MeOH solution of Ni(OAc)24H2O and
LH2 in 1:1 molar ratio for 4 h. The IR data are indicative of the dibasic tetradentate SNNS
51
donor nature of LH2. The (NiN) and (NiS) frequencies occur between 433-474 cm-1
and 353-366 cm-1 respectively. A square-planar structure has been suggested to them.
The yellow-green, six-coordinate, non-electrolytes, [NiL(H2O)2] are obtaineded by
refluxing an EtOH solution of NiCl26H2O and LH2 (122; where R = R' = H; R = Me, R' =
H; R = Et, R' = H; R = 1-Pr, R' = H; R = H; R' = Me; R= R' = Me; R= Et, R' = Me; R = 1Pr, R' = Me; R = H, R' = Ph; R = Me, R' = Ph; R = Et, R' = Ph; R = 1-Pr, R' = Ph) in
equimolar ratio in the presence of AcONa for 3 h[100]. They are soluble in DMF, DMSO
and py. They are air-stable and do not lose weight on heating up to 105 oC for 2 h
indicating that H2O molecules are coordinated to the metal ion. The (NiN) and (Ni
S) frequencies occur between 520-560 and 420-425 cm-1 respectively. The occurrence of
three bands between 8333-9910, 13250-16000 and 24380-26670 cm-1 due to the 3A2g
3
T2g(1), 3A2g 3T1g(F)(2) and 3A2g 3iT1g(P)(3) transitions respectively, the value of
2/1 (1.62-1.80) and magnetic moments (2.89-3.50 B.M.) of the compounds indicate the
presence of high-spin octahedral Ni(II) in a distorted octahedral environment. They are
more effective towards B. cirrafigellosus, E. coli, C. albicans and A. niger than LH2.
E.

The syntheses of two monomeric, golden-yellow, five-coordinate, low-spin
compounds, [Ni(LH)] and [Ni(L'H)] [here LH3 = 106; A = NH, R = R' = H; L'H3 = 106; A
= NH, R = H, R' = Me] have been reported[101]. The compounds on dissolution in py form
high-spin, six-coordinate, pseudo-octahedral adducts, [Ni(LH)py] and [Ni(L'H)py]
respectively. The ligands act as the dibasic pentadentate ONNNO donors. Their magnetic
moments are ~12 B.M.
The synthesis of a monomeric, pale-green, low-spin, five-coordinate compound,
[NiL] [where LH2 = 106; A = S, R = R' = H] has been reported[102]. Its magnetic moment
is 11 B.M. On dissolving in py, [NiL] forms a high-spin, six-coordinate, pseudooctahedral adduct, [NiLpy]. LH2 functions as a dibasic pentadentate ONSNO donor ligand.
The syntheses of monomeric, six-coordinate, 1:1 electrolytes (in MeNO2),
[NiX(LH)]X and [NiY(LH)](PF6) (here LH = 123; X = Cl, Br, I, NO3, SCN, Y = Cl, Br,
NO3 and SCN) has been reported[103]. LH acts as a neutral pentadentate N5 donor ligand.
The Ni(II) ions acquire a pseudo-octahedral environment in the compounds.
52
The green/light-green, monomeric, six-coordinate, 1:1 electrolyte (M = 88-106
mho cm2 mol-1 in DMSO), [Ni(LH2)X]X and non-electrolyte (M = 17 mho cm2 mol-1 in
DMSO) compound, [Ni(SO4)(LH2)] [where LH2 = 107; X = NO3, Cl, OAc] have been
synthesized[78]. LH2 acts as a neutral pentadentate NNSNN donor ligand coordinating
through its imino N, azomethine N and S atoms. The compounds display the (NiN) and
(NiS) vibrations between 384-479 and 313-343 cm-1 respectively. The nitrato, acetato
and sulphato groups are coordinated in a monodentate manner. The compounds display the
3
A2g(F) 3T2g(F)(1), 3A2g(F) 3T1g(F)(2) and 3A2g(F) 3T1g(P)(3) transitions
between 11135-12108, 18621-19416 and 21413-27322 cm-1 respectively corresponding to

their octahedral geometry. The spectral parameters [10Dq (11135-12108 cm-1), B' (419830 cm-1), (0.40-0.79), LFSE (159.6 to 173.6 kJ mol-1)] account for their covalent
nature. The molecular ion, isotopic peaks and base peaks appear at m/z = 602, 603 (M+ +
1) and 214 respectively. Their magnetic moments lie between 2.82-2.93 B.M. They show
enhanced antibacterial activity against X. compestris, P. aeruginosa and antifungal activity
against A. niger, F. oxysporum and A. brassicae than LH2.
The synthesis of a monomeric, five-coordinate, 1:2 electrolyte, [NiL]X2 (where L
= 2,6,10-triaza-1,11-bis(2-aminophenyl)undeca-1,10-diene, X = Cl, Br, I, NO3 and ClO4)
has been reported[104]. L functions as a neutral pentadentate ligand. A distorted squarepyramidal geometry has been suggested for the compound.
F.
With hexaadentate ligands:

Two monomeric, six-coordinate compounds, [NiL] (here LH2 =1,3-bis(o-
salicylaldiminophenylthio)propane)
and
[NiL']
(here
L'H2
1,2-bis(o-
salicylaldiminophenylthio)xylene) have been synthesized by the reaction of the

respective ligand and NiCl26H2O and Ni(ClO4)2 respectively[105]. The ligands act as the
dibasic hexadentate N2S2O2 donors.
Coordination compounds of copper(II)

Copper (Cu) is a peach coloured d-block transition element belonging to Group 11
and Period IV of the Periodic Table. Its atomic number, atomic weight and the electronic
configurations are 29, 63.54 amu and [Ar] 3d104s1 respectively. It has high thermal and
electrical conductance. Its common oxidation states are +1, +2, +3 and +4. In +2 state, it is
53
essential trace nutrient in biological systems. Cu is transported in the blood stream on a
plasma protein called ceruloplasmin, found as cofactor in several enzymes such as
cytochrome oxidase, superoxidedismutase, O2 transporting hemocyanin and in biological
electron transport in the form of protein including azurin and plastocyanin. In a squareplanar Cu(II) coordination compound, g|| > g > 2 and the unpaired electron resides in the
dx2 y2 orbital with 2B1g as the ground state[106], while when g > g||, the unpaired electron
resides in the dz2 orbital and 2A1g becomes the ground state. The dimeric Cu(II) compounds
display an additional weak signal typical of CuCu interaction at half-field corresponding
to Ms = 2 forbidden transition indicating the presence of the magnetic exchange
interaction in these. A value of 2Cu = 0.5 indicates the complete covalent bonding, while
the value of 2Cu = 1.0 suggests complete ionic bonding[107]. The coordination
stereochemistry around the Cu(II) ion in a given five-coordinate compound may be
deduced from the examination of the ESR spectral features. The two basic configurations
normally adopted by a five-coordinate compound are square-pyramidal or trigonalbipyramidal fashions. These configurations are characterized by the ground state dx2 y2 and
dz2 respectively[108]. The ESR spectrum of the Cu(II) compound provides a very good basis
for distinguishing between these ground states. The ESR spectral pattern for squarepyramidal Cu(II) compounds (dx2 y2 ground state) is quite different from that observed for
trigonal-bipyramidal (dz2 ground state). In frozen solution, square-pyramidal compounds
are characterized by an axial pattern g|| > 2.1 > g > 2.0 and A|| = 1.2-1.5 10-2 cm-1, while
the compounds with trigonal-bipyramidal structure show reversed axial pattern[109] i.e., g
> g|| ~2.0 and A|| = 6.0 10-3-1.0 10-2 cm-1. The geometric parameter (G), a measure of
the exchange interaction between the copper centers is calculated using the equation, G =
(g || 2.0023)/(g 2.0023). T he value of G = 4.4 indicates a dx2
ground state
having considerable exchange coupling[110]. The covalent nature of the metal-ligand bond
is indicated by g and 2Cu values. The Cu(II) ion belongs to the S = system and since its
spin-orbit coupling constant is negative[111], the magnetically dilute Cu(II) coordination
compound is expected to exhibit magnetic moment higher than the spin-only value of 1.73
B.M. due to the presence of orbital contribution[112]. A decrease in magnetic moment
generally occurs due to the antiferromagnetic exchange via overlap of metal-orbital with
54
the orbitals of the bridging O atoms. The ability of Cu(II) ion to form the coordination
to Cu(II) ion in a monodentate, bidentate, tridentate, tetradentate, pentadentate and
hexadentate fashion. We present here a brief survey of the Chemistry of coordination
compounds of Cu(II) ion.
A.

An air-stable, non-hygroscopic, non-electrolyte (in DMF), brown, four-coordinate
compound, [Cu(SO4)L2]2H2O (where L = 110; R = 3-NO2, X = O) is obtained by

refluxing a MeOH solution of CuSO45H2O and L in 1:2 molar ratio for 4 h[81]. It
decomposes between 200-205 oC. It is soluble in MeOH, EtOH and DMF. L acts as a
neutral monodentate N donor ligand. The suphato group coordinates in a bidentate
manner. The occurrence of two bands at 14520 and 15080 cm-1 due to the 2B1g 2B2g and
2
B1g 2Eg transitions and the magnetic moment (2.40 B.M.) of the compound suggest its
square-planar geometry. It exhibits higher fungistatic activity against A. niger, A. solani,

A. carneus and C. capsici than the ligand.
B.

A green, four-coordinate compound, [Cu(LH)2]EtOH (here LH2 = 35A-35C) is
obtained by stirring an EtOH solution of Cu(OAc)2H2O and LH2 in 1:2 molar ratio for 12
h[11]. It is soluble in Me2CO but insoluble in EtOH. It melts at 287 oC. Although LH2 is
potentially a dibasic tridentate OON donor ligand, but behaves as a monobasic bidentate
ON donor ligand. The band at 15038 cm-1 is due to a d-d transition for square-planar
geometry. The magnetic moment of the compound is 1.76 B.M. The appearance of a
signal at g = 1.807 and a shoulder at g = 1.859 indicates the square-planar geometry
distorted towards tetrahedral.
When an EtOH solution of CuCl22H2O and LH (80) is refluxed in 1:2 molar ratio
for 2 h, a four-coordinate, non-electrolyte (in EtOH), [CuL2] is obtained[51]. LH acts as a
monobasic bidentate ON donor ligand. The lower value of magnetic moment (1.51 B.M.)
of the compound than the spin-only value (1.73 B.M.) is due to the mixing of orbitalangular momentum from excited state via spin-orbit coupling. The appearance of a band at
21881 cm-1 due to the 2B1g 2A1g transition supports its square-planar geometry. The ESR
spectrum at 77 K displays four well-resolved peaks of low intensities in the low-field
55
region and one intense peak in the high-field region. The absence of a band due to Ms =
2 transition rules out the CuCu interaction. The ESR spectral data are: A|| = 1.4 x 10-2
cm-1, A = 4.7 10-3 cm-1, Aiso = 7.8 10-3 cm-1, g|| = 2.328, g = 2.067, giso = 2.15, 2 =
0.81 and 2 = 1.4. The greater value of g|| than g indicates the presence of unpaired
electron in the
dx2y2 orbital for square-planar geometry around Cu(II) ion. Its
antibacterial activity against S. aureus, B. subtilis, E. coli and A. niger is higher than LH.
Desai et al.[83] have synthesized the non-electrolyte heterochelates, [Cu(LH)L']
(112; R = H, R' = H, Cl, NO2; R = Cl, R' = H; R = Br, R' = H; R = NO2, R' = H, Cl, MeO;
R = Me, R' = H; R = MeO, R' = H; R = EtO, R' = H, L'H = pentane-2,4-dione M = Cu).
They are soluble in glacial acetic acid. The IR data are indicative of the monobasic
bidentate nature of LH2 and L'H.
A MeOH solution of Cu(OAc)2H2O and LH3 (81; R = OH, R' = H) or L'H4 (81; R
= R' = OH) in 1:2 molar ratio on refluxing for 1 h produce a greenish-brown, nonelectrolyte (M = 2.4 mho cm2 mol-1), four-coordinate compound, [Cu(LH2)2]H2O or
brown, non-electrolyte (M = 4.1 mho cm2 mol-1) compound, [Cu(L'H3)2]3H2O
respectively[52]. They are soluble in DMF, DMSO and THF. The former melts at 235 oC,
while the latter at 293 oC. Both the Schiff bases act as the monobasic bidentate ON donor
ligands. The (CuO) and the (CuN) vibrations occur at 505 and 435 cm-1 in
[Cu(LH2)2]H2O, while at 465 and 420 cm-1 in [Cu(L'H3)2]3H2O respectively. The
magnetic moments of [Cu(LH2)2]H2O and [Cu(L'H3)2]3H2O are 1.81 and 1.83 B.M.
respectively suggesting their square-planar geometries around the metal ions. The TG
curves of [Cu(LH2)2]H2O and [Cu(L'H3)2]3H2O exhibit the weight loss corresponding to
adsorbed H2O molecule(s) between 55-80 oC and 60-95 oC respectively. The appearance
of an endothermic peak at 65 oC and 80 oC in the DTA curves of the above compounds
respectively indicates the loss of hydrated H2O molecules. The endothermic peaks at 235
o
C and 293 oC respectively correspond to their melting points. At the high temperatures,
these compounds decompose to the metal oxide with the loss of organic skeleton.
The reaction of 2-aminophenol with Cu(II) ions produces[4] the aminophenolate
coordination compound as precipitate (in solution), which on further treatment with
4-benzyloxybenzaldehyde or but-2-enal in 1:1:1 molar ratios yields the brown compounds,
[CuL2] or [CuL'2] respectively (LH = 28 and L'H = 29). [CuL2] and [CuL'2] melt at 200
56
and 220 oC respectively. Both LH and L'H act as monobasic bidentate ON donor ligands.
[CuL2] displays the (CuO) and (CuN) vibrations at 500 and 440 cm-1 respectively,
while [CuL'2] displays these vibrations at 550 and 440 cm-1 respectively. The presence of a
band at 20000 and 18182 cm-1 in [CuL2] and [CuL'2] respectively due to the 2Eg 3T2g
transition and the values of their magnetic moments (1.85 and 1.92 B.M.) indicate their
square-planar geometries. [CuL2] displays the molecular ion peak at 667 (M+) and other
peaks
at
576
(MC6H5CH2)+,
457
(MC6H5CH2HOC6H4CN)+,
302
(100%,
C6H5CH2OC6H4CN==C6H4O)+, 199 (C6H5CH2OC6H4O)+, 91 (C6H5CH2)+ and 77

(C6H5). [CuL'2] shows the molecular ion peak at 383 (M+) and 160 (100%,
MeCHCHCHNC6H4O)+. Their biologically activity against S. dysenteria, E. coli, P.
aeruginosa, B. subtilis, S. lutea and S. aureus) is better than 2-aminophenol.
A green, six-coordinate, non-electrolyte (M = 10.1 mho cm2 mol-1 in DMSO),
polymeric compound, [CuCl2(LH)(H2O)]n (here LH = 84; R = H, R' = Me) has been
synthesized by refluxing an H2O/EtOH solution of CuCl22H2O and LH in 1:1 molar ratio
for 1 h[56]. It is insoluble in Me2CO, CHCl3 and C6H6 but is fairly soluble in DMF and
DMSO. It melts between 230-232 oC. LH acts as neutral bidentate ON donor ligand. The
appearance of a broad band at 14044 cm-1 due to the 2Eg 2T2g(D) transition supports its
octahedral geometry. Its magnetic moment is 1.86 B.M. indicating the presence of an
unpaired electron. It shows higher antibacterial activity against E. coli than LH, whereas
its antifungal activity against A. niger is less than LH. An octahedral polymeric structure
(99, M = Cu) has been assigned to it.
The synthesis of a six-coordinate, dinuclear, non-electrolyte, [Cu2L2(H2O)4] (where
LH2 = 87; R = H, 5,6-benzo) has been reported[58]. It is greenish-yellow (when R = H) and
grey (when R = 5,6-benzo). They are amorphous in nature, having high melting point and
feebly soluble in DMF and dioxane. The compound (when R = H) is stable up to 180 oC.
The coordinated water molecules and 1/5th of the ligand are lost between 180-220 oC. CuO
is the final product formed at 1000 oC. The IR data indicate the monobasic bidentate ON
donor nature of the ligand per metal ion coordinating through its phenolic O and
azomethine N atoms. The sulphone O atom(s) are not involved in coordination as evident
from the occurrence of the as(O==S==O) and the s(O==S==O) stretches at the same
energy (1150-1155 and 1320-1330 cm-1) in LH2 and the compounds respectively. The
57
(CuO) and the (CuN) vibrations occur at 505, 345 and 510, 350 cm-1 respectively.
They display an asymmetric broad band at 13450-14875 cm-1 with maxima at ~14250 cm-1
due to the 2Eg 2T2g transition. Both Jahn-Teller distortion and mixed ON donor atoms
contribute to the broadening of the absorption band, suggesting their distorted-octahedral
geometries. Their sub-normal magnetic moments (1.30 and 1.35 B.M.) indicate MM
interactions in a polymeric structure. The unpaired electron of the d-orbital of the metal
ion overlaps with the -orbital of the N atom of the azomethine moiety of the ligands. Due
to the high electron density of the N atoms, an electron from N moves to partially
occupied d-orbital of the metal ion with antiparallel spin to the original d-electron. Thus,
the magnetic moments are aligned antiparallel and are responsible for partial quenching of
paramagnetism due to the super-exchange phenomenon. Their ESR spectra are isotropic
possessing a single line characteristic of regular geometry resulting either due to pseudorotational type of Jahn-Teller distortion or due to the extensive exchange coupling
operating between the Cu(II) ions in a dinuclear structure. The geometry around the metal
ions in the unit cell of the compound (when R = H) is tetragonal (elongated octahedral)
with g = 2.0578 and g = 2.1618. The axial symmetry parameter (G) is 2.79 indicating
the strong exchange interaction among the magnetically equivalent Cu(II) ions in the unit
cell. The gav value of the compound (when R = 5,6-benzo) is 2.0678. A dinuclear,
octahedral structure (88; R = H, 5,6-benzo, M = Cu, A = H2O) has been suggested to them.
A dark-blue, six-coordinate, non-electrolyte (M = 22.0 mho cm2 mol-1 in DMSO),
[CuCl2(LH2)2] (here LH2 = 84; R = 4-OH, R' = Me) has been synthesized by refluxing an
H2O/EtOH solution of CuCl22H2O and LH2 in 1:1 molar ratio for 8 h[56]. It is fairly
soluble in DMF and DMSO. It decomposes between 210-212 oC. LH2 acts as a neutral
bidentate ON donor ligand. The compound displays one broad band at 16110 cm-1 due to
the 2Eg 2T2g(D) transition supporting its octahedral geometry. Its magnetic moment is
1.88 B.M. indicating the presence of an unpaired electron. It shows higher antibacterial
activity against E. coli than LH2, whereas its antifungal activity against A. niger is less
than LH2. An octahedral structure (89, M = Cu) has been assigned to it.
An EtOH solution of Cu(OAc)2H2O and LH2 (30, R = H) in 1:2 molar ratio upon
refluxing in the presence of TEM produce[6] a red, non-electrolyte (M = 19 mho cm2
58
mol-1), four-coordinate compound, [Cu(LH)2]. It decomposes at 272 oC. LH2 acts as a
monobasic bidentate ON donor ligand.
Although LH (124; R = R'' = H, R' = OH) is potentially a monobasic tetradentate
ONNS donor ligand, it behaves[113] as a monobasic bidentate ON donor ligand in a coffeebrown, four-coordinate, non-electrolyte (M = 14.04 mho cm2 mol-1 in MeOH), [CuL2].
The ring N and S atoms do not participate in the coordination. Its magnetic moment is
1.78 B.M.
On refluxing an EtOH solution of CuCl22H2O and an H2O-EtOH solution of
NaLH (89) in 1:1 and 1:2 molar ratios, air and moisture-stable, intense-coloured,
amorphous, four-coordinate compound, [Cu(LH)(H2O)2]Cl and another four-coordinate
compound, [Cu(LH)2] are obtained respectively[59]. They are insoluble in common organic
solvents and soluble in H2O, DMF and DMSO. The carboxylato group coordinates in a
monodentate fashion. NaLH behaves as a monobasic bidentate ON donor (carboxylic O
and endocyclic N of -lactam ring) ligand. The presence of (CuO) stretch at 525 cm-1
and (CuN) stretch at 410 cm-1 also indicates the bonding through O and N atoms. The
magnetic moments of the compounds are 1.5 and 1.6 B.M. respectively indicating the
antiferromagnetic spin-spin interaction through molecular association. They show
antibacterial activities higher than the ligand against E. coli, K. pneumoniae, P. mirabilis,
P. aeruginosa, S. typhi, S. dysentriae, B. cereus, C. diphtheriae and S. pyogenes. The
structures, 125 for [Cu(LH)(H2O)2]Cl and 126 for [Cu(LH)2] have been assigned.
A brown, four-coordinate compound, [Cu(LH)2]H2O is obtained by refluxing an
EtOH solution of Cu(OAc)2H2O and LH2 (52; R = (2-OH)C6H4CH, R' = NHC6H5, X = S)
in 1:1 molar ratio[114]. LH2 behaves as a monobasic bidentate NS donor. The phenolic O
atom does not take part in coordination. Its magnetic moment is 1.51 B.M. It has a LMCT
band at 25970 cm-1 and a d-d transition band at 15640 cm-1 respectively. The values for g||
> g > 2.003 and G = 3.55 are consistent with dx2-y2 ground state.
An aqueous solution of Cu(OAc)2H2O on treating with an hot EtOH solution of
LH [127; R = 4-NMe2, R' = H, R'' = Et] in 1:2 molar ratio forms[115] a light-yellow, sixcoordinate compound, [CuL2(H2O)2]. It is insoluble in common organic solvents and does
not melt even up to 300 oC. LH acts as a monobasic bidentate NS donor ligand. The
59
compound is interestingly diamagnetic owing to the reduction of Cu(II) to Cu(I) in the
presence of excess of ligand.
On refluxing an EtOH solution of CuCl22H2O and LH2 (92) in 1:2 molar ratio for
1 h at pH = 6, a six-coordinate, non-electrolyte (M = 12.6 mho cm2 mol-1 in Me2CO),
[Cu(LH)2(H2O)2] is produced[61]. It is soluble in common organic solvents. The Schiff
base acts as a monobasic bidentate NN donor ligand. The (CuN) vibrations occur at
440 cm-1. The appearance of a broad band at 16638 cm-1 due to the 2Eg 2T2g transition
and the magnetic moment (1.9 B.M.) suggest a distorted octahedral geometry around the
metal ion. At LNT, it shows four well resolved peaks with low-field region. The g|| (2.31)
and g (2.16) values indicate that the ground state is predominantly dx2y2. The covalence
parameter (2 = 0.82) indicates that the compound has some covalent character in the
ligand environment.
C.

Sallam et al.[62] have reported the syntheses of the green coordination compounds,
[Cu(LH)2] [here LH2 = 93; R' = R'' = Ph, A = (CH2)2; R' = Ph, R'' = Me, A = (CH2)2; R' =
Me, R'' = Ph, A = 1,2-C6H4], [Cu(L'H)2]2H2O [here L'H2 = 93; R' = R'' = Ph, A = 1,2C6H4], a blue compound, [Cu(L''H)2]2H2O [here L''H2 = 93; R' = R'' = Me, A = (CH2)2], a
brown compound, [Cu(L'''H)(OH)] [here L'''H2 = 93; R' = R'' = Me, A = 1,2-C6H4] and a
grey compound, [Cu(L1H)(OH)]2H2O [here L1H2 = 93; R' = CF3, R'' = thienyl, A = 1,2C6H4]. The IR data are indicative of the monobasic tridentate ONO donor behaviour of the
ligands. The (CuO) and the (CuN) vibrations occur between 621-654 cm-1 and 440596 cm-1. [Cu(LH)2] [when LH2 = 93; R' = R'' = Ph, A = (CH2)2] shows a band at 15948
cm-1 due to the 2Eg 2T2g transition indicating an octahedral structure. [Cu(LH)2] [R' =
Ph, R'' = Me, A = (CH2)2] and [Cu(L''H)2]2H2O [R' = R'' = Me, A = (CH2)2] adopt
distorted octahedral structures as evident by the appearance of two bands at 14836, 17667
and 14792, 18484 cm-1 due to the 2B1g 2A1g and 2B1g 2Eg transitions respectively.
[Cu(LH)2] [R' = R'' = Ph, A = (CH2)2] in dioxane shows g|| = 2.082 and g = 2.05
indicating the strong interaction between the ligand and the metal. The magnetic moment
of [Cu(LH)2] [when R' = R'' = Ph, A = (CH2)2] is 1.6 B.M. and that of [Cu(L'''H)(OH)]
[here R' = R'' = Me, A = 1,2-C6H4] is 1.3 B.M. These values are less than the spin-only
value (1.73 B.M.), which may be due to an antiferromagnetic effect, the influence of spin-
60
orbital coupling in the ground state for spin-doublet species or due to the formation of
dimeric or polymeric structures. The magnetic moments of rest of the compounds lie
between 2.0-2.5 B.M. respectively. [Cu(LH)2] [when R' = Ph, R'' = Me, A = (CH2)2] has
an exothermic peak between 180-243 oC indicating the loss of two Me and two Ph groups.
Further decomposition occurs between 370-526 oC. CuO is the final product formed.
Kumar et al.[10] have synthesized a dark-brown, polystyrene-anchored fourcoordinate compound, [PSCH2LHCuDMF] (where PSCH2LH3 = 34) by refluxing a
DMF swollen suspension of PSCH2LH3 and a DMF solution of Cu(OAc)2H2O. The PRC
of the compound is 57.6 and the MBC of PSCH2LH3 is 0.39 mmol of Cu per g of the
ligand. PSCH2LH3 behaves as a dibasic tridentate ONO donor ligand. The magnetic
moment (2.18 B.M.) and the appearance of broad band at 16800 cm-1 due to the 2B1g
2
A1g, 2B2g, and
Eg transitions is indicative of a distorted square-planar structure around
the metal ion. The spectral parameters: g||, g, 2, Pd and are 2.24, 2.07, 0.76, 1.82 x 10-2
cm-1 and 0.42 respectively.
Emara et al.[41] have reported the synthesis of a green, four-coordinate compound,
[Cu2L(MeOH)2] (where LH4 = 70, X = OH). It is soluble in common organic solvents but
partially soluble in DMF and DMSO. The IR data are indicative of bis(dibasic tridentate)
ONO donor nature of LH4. The (CuO) and the (CuN) vibrations occur at 612 and
530 cm-1 respectively. Its magnetic moment is 1.36 B.M. indicating the partial coupling of
unpaired electrons between neighbouring Cu(II) ions in the solid state.
A brown, four-coordinate compound, [CuL(H2O)]H2O (where Na2LH2 = 94; R =
H) and another black, four-coordinate compound, [CuL'(H2O)]H2O (where Na2L'H2 = 94;
R = 3-OMe) are obtained by refluxing an EtOH solution of CuCl22H2O and an aqueous
solution of LH2 or L'H2 respectively in 1:1 molar ratio[63]. They are non-electrolytes (M =
13.2 and 14.7 mho cm2 mol-1) in aqueous solution. They melt at 225 and 240 oC
respectively. The IR data indicate a dibasic tridentate ONO donor behaviour of the
ligands. Their magnetic moments are 1.7 B.M. indicating a tetrahedral environment
around the metal ions. [CuL(H2O)]H2O remains stable up to 60 oC. The loss of noncoordinated and coordinated H2O molecules takes place between 60-100 oC and 125-195
o
C respectively. The decomposition of organic skeleton occurs between 370-582 oC and
finally CuO is obtained. In [CuL'(H2O)]H2O, the loss of non-coordinated and coordinated
61
H2O molecules takes place between 65-105 oC and 130-205 oC respectively. Here, the
decomposition of organic skeleton occurs between 315-590 oC and finally CuO is
obtained.
The green, six-coordinate heterochelates, [CuLL'(H2O)] (where LH2 = 96; R = R''
= H, R' = OH, R''' = Me, L' = ophen) and [CuLL'(H2O)]3H2O (where LH2 = 96; R = R'' =
H, R' = OH, R''' = 128; L' = ophen) have been synthesized by stirring a MeOH solution of
LH2, L' and an aqueous solution of CuCl22H2O in 1:1:1 molar ratios[116]. They melt at 110
and 78 oC respectively. Their molar conductances are 24.5-42.8 mho cm2 mol-1. LH2
behaves as a dibasic tridentate ONO donor ligand. They display the 2Eg 2T2g transition
at 16667 and 16393 cm-1 respectively. The former heterochelate exhibits lesser
antibacterial activity against E. aerogene, B. cereus and B. megaterum than the ligand. A
distorted octahedral structure (129; R = Me, 128, M = Cu) has been suggested for the
heterochelates.
The syntheses of a green, dimeric coordination compound, [Cu2L2], a brown, fourcoordinate compound, [CuCl(LH)], a pale-green compound, [Cu2(SO4)(LH)2] and two
pale to dark-green, monomeric adduct/heterochelate, [CuLB] and [CuL(BB')] (here LH2 =
52; R = (2-OH)C6H4C(Me), R' = NHC6H5, X = O, B = py, BB' = ophen) have been
reported[117]. The compounds/adduct/heterochelate are non-electrolytes and soluble in
DMF, DMSO and MeCN. LH2 behaves as a monobasic tridentate ONO donor in
[CuCl(LH)], [Cu2(SO4)(LH)2]; dibasic tridentate ONO donor in [Cu2L2], [CuLB] and
[CuL(BB')]; B as a neutral monodentate N donor and BB' as a neutral bidentate NN donor
in the above compounds. The appearance of the bands at 997, 1039 and 1119 cm-1
indicates the bidentate bridging fashion of sulphato group. The trend of g|| > g suggests a
square-planar geometry of [CuCl(LH)]. Their magnetic moments lie between 1.71-1.93
B.M. [CuL(BB')] crystallizes in a monoclinic fashion with lattice parameters: a = 13.4877
, b = 25.891 , c = 14.1496 , = = 90.0o and = 113.73o. A distorted square-planar
and a distorted square-pyramidal structure have been assigned to [CuLB] and [CuL(BB')]
respectively.
An air-stable, four-coordinate, non-electrolyte, [CuCl(LH)]2H2O (here LH2 = 39)
has been synthesized by stirring a MeOH solution of NaLH and CuCl22H2O in 2:1 ratio
for 8 h at room temperature[13]. It is soluble in DMSO and DMF and slightly soluble in
62
MeCN. The ligand behaves as a monobasic tridentate OON donor. The carboxylato group
coordinates in a monodentate fashion. The rather high value of the magnetic moment (2.0
B.M.) is due to the mixing of spin-orbital coupling with the ion levels of identical
multiplicity. The value of gll (2.17) > g (2.08) indicates that the unpaired electron resides
in the dx2y2 orbital having 2B1g as a ground state term. It exhibits a broad band centered at
14285 cm-1 which corresponds to the 2B1g 2A1g transition in a square-planar or distorted
tetrahedral geometries. It shows higher activity than LH2 against S. aureus, P. mirabilis, K.
pneumoniae, S. enteriditis, P. aeruginosa and E. coli. A tetrahedral structure (40, M = Cu)
has been assigned to it.
The syntheses of air-stable, non-hygroscopic, non-electrolyte, dimeric, sixcoordinate compounds, [CuClL(H2O)]2 (here LH = 43; R = Me, Et, propyl) and
[CuCl(L'H)(H2O)]2 (L'H2 = 43; R = CH2CH2OH) have been reported[16]. They are soluble
in DMF and DMSO. The coordinated water molecules are lost between 190-200 oC.
Although L'H2 is potentially a dibasic tetradentate NONO donor ligand but similar to LH,
it also behaves as a monobasic tridentate NON donor ligand bridging through its enolic O
atom. The existance of a band between 16583-16666 cm-1 due to the 2Eg 2T2g transition
indicates their distorted octahedral geometries. Their magnetic moments lie between 1.631.79 B.M. They exhibit higher antifungal activity against A. niger than the corresponding
ligands. A distorted octahedral structure (44; M = Cu) has been suggested for them.
A blue, nano-crystalline, four-coordinate complex, [CuL(H2O)]Cl (where LH = 97)
has been synthesized by refluxing a MeOH solution of CuCl2xH2O and LH in 1:1 molar
ratio for 2 h[66]. The complex is 1:1 electrolyte (M = 85 mho cm2 mol-1 in MeOH). It is
soluble in DMF and DMSO. The ligand behaves as a monobasic tridentate NON donor
coordinating through its azomethine N, carboxylato O and imidazole N atoms. The
magnetic moment (1.83 B.M.) and the existence of a band at 15385 cm-1 due to the 2B1g
2
B2g transition indicate a square-planar environment around the metal ion. The loss of
coordinated H2O molecule, Cl- ion (as HCl gas) and organic skeleton occur between 214230, 251-272 oC and 405-550 oC. Finally CuO is obtained as residue. The complex
exhibits moderate effectiveness than LH.
Biswas et al.[118] have synthesized a reddish-blue, four-coordinate, dimeric
heterochelate, [(CuL)2(AA)](BF4)2 by refluxing an MeOH solution of Cu(BF4)26H2O, LH
63
and AA (here LH = 130; R = R' = Me, R'' = (CH2)2NH2, AA = -4,4'-bipy) in 2:2:1 molar
ratio. LH behaves as a monobasic tridentate ONN donor ligand. The heterochelate
crystallizes in a monoclinic fashion with a = 8.345 , b = 10.178 , c = 17.519 , = =
90.0o, = 95.24o and Z = 2. A distorted square-planar geometry has been assigned to the
heterochelate.
Adhikary et al.[119] have reported the synthesis of a monomeric, four-coordinate,
black compound, [CuL(N3)] (where LH = 131; R = R' = H, R'' = (CH2)2NEt2) and another
polymeric, five-coordinate, black compound, [CuL'(-1,3-N3)]n (where L'H = 131; R = R'
= H, R'' = (CH2)2NMe2). The Schiff bases are coordinated to the metal ion through their
phenolic O, azomethine N and amine N atoms. The fourth coordination site in the former
is occupied by azido group. The Cu(II) ions are bridged through -1,3-azido ligands in
end-to-end fashion forming infinite chain structure in the polymeric compound. The
monomeric compound crystallizes in a monoclinic fashion with a = 6.69 , b = 13.04 , c
= 17.13 , = = 90, = 97.19 and Z = 4. The polymeric compound crystallizes in an
orthorhombic fashion with a = 14.56 , b = 18.53 , c = 19.26 , = = = 90 and Z =
4. A square-planar structure for the former and a distorted square-pyramidal structure for
the latter have been assigned.
The synthesis of the bluish-green, dimeric, four-coordinate, non-electrolyte, [CuL]2
(132; Y = O, COO) has been reported[55]. They are soluble in DMF and DMSO, partially
soluble in MeCN and CHCl3. The Schiff bases act as the dibasic tridentate ONN donor
ligands. The carboxylato group coordinates in a monodentate mode. They display a broad
band at
~12800 cm-1 due to the 2B1g 2B2g transition in a distorted square-planar
structure indicating distortion due to dimerization. The dimeric compound contains seven
hyperfine lines in parallel components due to an intramolecular exchange interactions.
A dark-green, four-coordinate, dinuclear compound, [Cu2L(MeOH)2](NO3)2
(where LH2 = 70; X = NH2) is obtained by refluxing a MeOH solution of
Cu(NO3)22H2O and LH2 in 2:1 molar ratio for 1 h[41]. It is soluble in common organic
solvents but partially soluble in DMF and DMSO. The IR data are indicative of
bis(monobasic tridentate) ONN donor nature of LH2. The (CuO) and the (CuN)
vibrations occur at 604 and 525 cm-1 respectively. The appearance of two new bands at
1384 and 856 cm-1 in it indicates the presence of ionic nitrate group. Its magnetic moment
64
is 1.98 B.M. The appearance of a band at 14771 cm-1 due to the E T transition and the
value of g = 2.1005 suggest a tetrahedral environment around the metal ion.
Shit et al.[120] have synthesized the dark-green, block shaped crystalline, end-to-end
doubly bridged, five-coordinate, dinuclear compound, [CuL(1,3N3)2]2 [where L = 133; R
= Me, R' = CH2COCF3, R'' = CH2CH2N(Me)2] by stirring a MeOH solution of
Cu(ClO4)26H2O and L with addition of NaN3 solution. L behaves as a neutral tridentate
ONN donor ligand. The appearance of the (N3) stretch at 2070 cm-1 and splitting in the
(N3) stretch at 635-610 cm-1 indicate the existence of a bridged azide group in the
compound. The latter is centro-symmetric dimer in which the metal ions are fivecoordinate, being bonded to three coordinate sites from L and two bridging azide ions in
end-to-end fashion making an intrametal CuCu distance of 5.096 within the dimeric
part, with an inversion centre placed midway between them. It crystallizes in a monoclinic
fashion with a =10.679 , b =9.706 , c = 13.635, = = 90o and = 107.9o. The endto-end bridging azido group is quasilinear with an NNN bond angle of 176.52o and a
bond length of azide ions are 1.1454 and 1.185 with CuNaxialN, 129.6 and Cu
NeqN, 118.3 respectively. The -(1,3)-azido group is linear with NNN bond
angle 176.5o. The end-to-end bridges form a closed and puckered eight-membered ring in
a stable chair form without any intramolecular covalent and H-bonding. The shape of plot
of mT vs T indicates the ferromagnetic coupling until 9.5 K, which results from
interaction of Cu(II) ions through the double end-to-end azide bridge. It shows two bands
at g|| = 2.16 and g = 2.07 which corresponds to the transition Ms = 1. A fivecoordinate distorted square-pyramidal geometry has been assigned to it.
Jadhav et al.[17] have observed that the green, six-coordinate complex, [CuL2] is
obtained on refluxing an hot MeOH solution of Cu(NO3)26H2O and LH (45) in 1:2 molar
ratio at pH = 7.5-8.5. The complex is non-electrolyte (M = 12.02 mho cm2 mol-1 in
DMSO). LH acts as a monobasic tridentate ONN donor ligand coordinating through its
phenolic O and both azomethine N atoms. The magnetic moment (1.84 B.M.) and the
appearance of a band at 13513 cm-1 due to the 2Eg 2T2g transition indicate the presence
of octahedral environment around the metal ions. The compound shows higher
antimicrobial activity against Gram-negative (E. coli) than Gram-positive (S. aureus)
bacteria.
65
The syntheses of a dark-brown, dimeric, four-coordinate compound, [CuL]2 and its
monomeric, four-coordinate py adduct, [CuL(py)] (here LH2 = 116; R = R' = H) have been
reported[90]. The compound and the adduct are air-stable and non-electrolytes in DMF.
[CuL]2 is insoluble in CHCl3, MeOH, EtOH and C6H6 indicating its dimeric or polymeric
nature. On the other hand, [CuL(py)] is fairly soluble in CHCl3, dioxane, C6H6 and DMF.
The IR data indicate the dibasic tridentate ONS donor nature of the ligand. The
coordination number four of [CuL]2 is completed by the ligand bridging through
deprotonated phenolic O atom. [CuL]2 displays sub-normal magnetic moment (1.2 B.M.)
indicating -bonding or super-exchange interaction in a dimeric state. [CuL(py)] shows
magnetic moment value of 2.01 B.M. at 304 K showing its magnetically dilute nature.
The complexation of a yellow colored benzothiazoline (LH2, 46A, 46B) with
Cu(II) ion proceeds with the rearrangement of benzothiazoline ring to form the
corresponding violet colored, non-electrolyte, [CuCl(LH)][20]. The benzothiazoline in the
presence of Cu(II) ion rearranges to form Schiff base. The latter coordinates in the keto
form as monobasic tridentate ONS donor. The magnetic moment (1.95 B. M.) and the
existence of a band at 20243 cm-1 suggest the square-planar geometry for the complex.
Seena et al.[114] have synthesized the brown, dimeric compounds, [(CuL)2]H2O
and [(CuL')2] by refluxing an EtOH solution of Cu(OAc)2H2O and LH2 or L'H2 (here LH2
= 52; R = (2-OH)C6H4CH, R' = NHC6H5, X = S and L'H2 = 52; R = (2-OH)C6H4CH, R' =
NHC6H11; X = S) in 1:2 molar ratio. The green, five-coordinate heterochelates,
[CuL(AA)]H2O and [CuL'(AA)] are obtained by refluxing an EtOH solution of
Cu(OAc)2H2O, the ligand (LH2 or L'H2) and AA (4,4'-dimethyl-2,2'-bipyridine) in 1:1:1
molar ratios respectively. LH2 and L'H2 behave as the dibasic tridentate ONS donor
ligands. The lower value of magnetic moment (~1.25 B.M.) of dimeric compounds than
the spin-free value indicates the presence of the anti-ferromagnetic spin-spin interaction
between the Cu(II) ions. They display LMCT bands between 24000-28000 cm-1 and a d-d
transition band between 14000-16000 cm-1 respectively. [CuL'(AA)] crystallizes in a
monoclinic fashion with a = 25.669 , b = 14.486 , c = 15.640 , = = 90.0o and =
95.678o. The g values for [(CuL)2]H2O, [CuL(AA)]H2O and [(CuL')2] are 2.059, 2.070
and 2.129 respectively. The values of g||, g and G (2.195, 2.063 and 3.17 respectively) for
[CuL'(AA)] are consistent with dx2 y2 ground state.
66
A four-coordinate, non-electrolyte (in DMSO), [CuCl(LH)] (where LH2 = 50; R =
OMe, R' = NH2) has been synthesized by stirring a MeOH solution of CuCl22H2O and
NaLH in 1:2 molar ratio for 8 h at room temperature[43]. It is air-stable and soluble in
DMF and DMSO and slightly soluble in MeCN. The carboxylato group is coordinated in a
monodentate fashion. The presence of (CuS) stretch at 300 cm-1 indicates coordination
through S atom of thiophene moiety. LH2 behaves as a monobasic tridentate OOS donor
ligand. The magnetic moment of the compound is 1.9 B.M. The value of g|| (2.19) > g
(2.07) indicates that the unpaired electron resides in the dx2
orbital having 2B1g as a
ground state term. It shows lesser bactericidal activity than the ligand against S. aureus, E.
faecalis, E. coli, S. sonnei, P. mirabilis and S. enteritidis. A distorted tetrahedral structure
(51; R = OMe, R' = NH2, M = Cu, A = nil) has been assigned to it.
The synthesis of a bluish-green, dimeric, four-coordinate, non-electrolyte
compound, [CuL]2 (132, Y = S) has been reported[55]. It is soluble in DMF and DMSO,
partially soluble in MeCN and CHCl3. The ligand acts as a dibasic tridentate NNS donor
ligand. The compound displays a broad band at 11700 cm-1 due to the 2B1g 2B2g
transition in a distorted square-planar structure indicating distortion due to dimerization.
The dimeric compound contains seven hyperfine lines in parallel components due to an
intramolecular exchange interactions. The spectral parameters: g||, g, gav, 2, ' and A are
2.28, 2.06, 2.17, 0.63, 380 and 9.0 x 103 cm-1 respectively. Its subnormal magnetic
moment (1.03 B.M.) is due to an antiferromagnetic exchange interaction arising from
dimerization with two planar Cu atoms side by side, linked by two S atoms which permits
an antiferromagnetic exchange interaction between the Cu atoms through S atoms. The
low value of magnetic moment in the present case is due to the interposition of S atoms
which withdraws the electron density from Cu ions into its empty d-orbitals.
A green, monomeric, four-coordinate, non-electrolyte, [CuClL] [here LH = 52; R =
C5H4N(CH), C5H4N(CMe), R' = NHC6H4(2-Me), NHC6H4(3-Me), NHC6H4(4-Me), X = S]
is obtained by refluxing an EtOH solution of CuCl22H2O and LH in 1:1 molar ratio[121].
LH acts as a monobasic tridentate NNS donor ligand. The magnetic moments of the
compounds lie between 1.73-2.03 B.M., indicating the presence of one unpaired electron
in them.
67
Ravoof et al.[122] have synthesized the air-stable, green crystalline, four-coordinate
compounds, [CuLA] (where LH = 52; R = C5H4N(CMe), C5H4N(CPh), R' = SCH2C6H5, X
= S, A = saccharinate anion, C7H4O3NS) by heating hot aqueous solution of
[CuA2(H2O)4]2H2O and LH in 1:1 molar ratio in EtOH for h. They are readily soluble
in DMF and DMSO. Their molar conductances are 9.31-27.4 mho cm2 mol-1. LH behaves
as a monobasic tridentate NNS donor ligand coordinating through its azomethine N,
thiomercapto S and pyridyl N atoms. The magnetic moments of the compounds are 1.81.87 B.M. They show low antibacterial and antifungal activity against M. staphylococcus,
B. subtilis, S. mutant, P. aeruginosa, C. albicans, A. ochraceous, S. ceciricaee and C.
lypolytica. They have higher activity against the leukemic cell line (HL-60) except the
compound (where R = C5H4N(CMe). They have no activity against the breast cancer cell
line (MCF-7). A distorted square-planar geometry has been assigned to them.
D.

A green, non-electrolyte (M = 8.3 mho cm2 mol-1), six-coordinate compound,
[CuL(H2O)2] is obtained by refluxing a mixture of an H2O/EtOH solution of

Cu(OAc)2H2O and a DMF solution of LH2 (26; R = 3-OMe, R' = OH, R'' = H, R''' = C2H4)
in 1:1 molar ratio for 4 h[2]. It decomposes at 300 oC and soluble in DMF and DMSO. The
Schiff base acts as a dibasic tetradentate ONNO donor ligand. The (CuO) and (Cu
N) vibrations occur at 530 an 460 cm-1 respectively. The compound exhibits a broad band
at 17605 cm-1 due to the 2E2g 2T2g transition. Its magnetic moment is 1.88 B.M.
indicating an octahedral environment around the metal ion.
The mononuclear, brown coloured compound [CuL] is obtained by stirring an
EtOH solution of Cu(OAc)2H2O and LH2 (104) in equimolar ratio[74]. LH2 behaves as a
dibasic tetradentate (ONNO donor) ligand. The complex exhibits a broad band at 15576
cm-1 due to the 2B1g 2A1g transition indicative of square-planar arrangement. The
complex crystallizes in a triclinic fashion with a = 7.999 , b = 10.0520 , c = 13.6974 ;
= 103.65o, = 95.965o, = 90.316o and Z = 2.

A trinuclear, non-electrolyte (M = 25.32 mho cm2 mol-1 in DMF),
[Cu2L2CuCl2]3H2O (134; A = H2O, LH2 = 101) has been synthesized[70]. It melts and
decomposes at 309 and 334 oC respectively. The appearance of a new band at 870 cm-1 is
indicative of CuOCu skeleton in it. LH2 acts as a dibasic tetradentate ONNO donor
68
ligand. The lower value of the magnetic moment (1.43 B.M.) of the compound indicates
the presence of CuCu interaction.
The syntheses of two green compounds, [CuCl2(LH4)] (where LH4 = 135) and
other [CuCl2(L'H2)] (here L'H2 = 136) have been reported[123]. They are insoluble in H2O,
MeOH, EtOH, Me2CO, C6H6, MeCN, CCl4 etc., however soluble in DMF, DMSO and
py. The former decomposes at 285 oC, while the latter melts at 248 oC. Their molar
conductances in DMF are 42.4 and 39.4 mho cm2 mol-1 respectively. The IR data indicate
the neutral tetradentate ONNO donor behaviour of the ligands. The coordinating sites in
case of LH4 are both the carbonylic O and azomethine N atoms, while in case of L'H2, they
are the hydrazidic O, azomethine N, py ring N and acetyl O atoms. The presence of a
single band at 12500 cm-1 in [CuCl2(LH4)] and at 13262 cm-1 in [CuCl2(L'H2)] due to the
2
Eg 2Tg transition (10Dq = 12500, 13262; LFSE = 89.40, 94.85 kJ mol-1) is indicative
of a distorted octahedral geometry around the metal ion.

The syntheses of four coordinate compound, [CuL] (here LH2 = 119; R = H, 5-Cl,
5-NO2, 3-OEt) has been reported[97]. The unsymmetrical tetradentate Schiff base
coordinates through its both phenolic O and the azomethine N atoms. The magnetic
moments of the compounds lie between 1.56-2.20 B.M. The compounds show broad
unsymmetrical band between 22831-24038 cm-1 due to the 2B1g 2A1g transition in
square-planar geometry. Thermal studies reveal a single step decomposition pattern due to
the loss of part of organic moiety.
An EtOH solution of Cu(OAc)2H2O and LH2 (105; R = H, Cl, Me) in 1:1 molar
ratio on refluxing for 4 h produce an air-stable, non-hygroscopic, non-electrolyte (M =
2.9-5.2 mho cm2 mol-1) [CuL][76]. The compound is soluble in DMSO. The ligand
coordinates to the metal ion through its carboxylic O, ethereal O, azomethine N and thione
S atoms. The compounds exhibit (CS) stretch between 613-634 cm-1. Their magnetic
moments lie between 1.39-1.82 B.M.
Beraldo et al.[99] have synthesized red/reddish-brown, four-coordinate compound,
[CuL] (where LH2 = 121; R = NHMe, NHEt, NMe2, piperidine) by refluxing a MeOH
solution of Cu(OAc)2H2O and LH2 in 1:1 molar ratio for 4 h. The IR data are indicative
of the dibasic tetradentate SNNS donor nature of LH2. The (CuN) and (CuS)
stretches occur between 450-476 cm-1 and 354-365 cm-1 respectively. Their magnetic
69
moments (1.5-1.8 B.M) and the occurrence of bands at 14000 and 18000 cm-1 due to the
2
B1g 2B2g and 2B1g 2A1g transitions respectively support the square-planar geometry

E.

A blue, monomeric, six-coordinate, non-electrolyte (M = 8.9 mho cm2 mol-1 in
DMSO), [Cu(LH3)(H2O)]2H2O [where LH5 = 106; R = 3-COOH, R' = H, A = NH) has

been synthesized[77]. It melts at 218 oC. LH5 acts as a dibasic pentadentate ONNNO donor
ligand. The magnetic moment of the compound is 1.89 B.M. The latter display bands at
14000 and 24000 cm-1 corresponding to the pseudo-octahedral geometry.
The synthesis of an air-stable, five-coordinate compound, [Cu(LH)]3H2O (here
Na2LH = 62) has been reported[35]. Na2LH behaves as a dibasic pentadentate ONOON
donor ligand. The energy difference ( = 245 cm-1) between as(COO) and s(COO)
stretches suggests the monodentate coordinating behaviour of the carboxylato group. The
non-coordinated H2O molecules are lost between 80-110 oC. Its magnetic moment is 2.2
B.M. It shows higher bactericidal activity against S. aureus, E. coli, S. sonnei, P. mirabilis,
S. enteritis and P. aeruginosa than LH2. A five-coordinate structure (63, M = Cu) has been
assigned to it.
The green, monomeric, six-coordinate, 1:1 electrolyte (M = 87-116 mho cm2 mol1
in DMSO), [CuX(LH2)]X and another non-electrolyte (M = 15 mho cm2 mol-1 in
DMSO), [Cu(SO4)(LH2)] [where LH2 = 107; X = NO3, Cl, OAc] have been synthesized[78].
LH2 acts as a neutral pentadentate NNSNN donor ligand coordinating through azomethine
N, imino N and S atoms. The compounds display the (CuN) and (CuS) vibrations
between 422-501 and 318-351 cm-1 respectively. The nitrato, acetato and sulphato groups
are coordinated in a monodentate manner. They display the 2B1g 2A1g(1), 2B1g
2
B2g(2) and 2B1g 2Eg(3) transitions between 12188-15479, 18621-19132 and 24402-
27322 cm-1 respectively, typical of their elongated tetragonal geometry and D4h symmetry
with the dx2 y2 ground state. The molecular ion, isotopic and the base peaks appear at m/z
= 602, 603 (M+ + 1) and 214 respectively. Their magnetic moments lie between 1.82-1.91
B.M. They show enhanced antifungal activity against A. brassicae, A. niger, F. oxysporum
and antibacterial activity against X. compestris, P. aeruginosa than the ligands.
70
The synthesis of monomeric, five-coordinate, 1:2 electrolyte, [CuL]X2 [where L =
(2,6,10-triaza-1,11-bis(2'-aminophenyl)-undeca-1,10-diene; X = Cl, Br, I, NO3 and ClO4]
has been reported[104]. L functions as a neutral pentadentate ligand. A distorted squarepyramidal geometry has been suggested for the compound.
F.

A MeOH solution of Cu(OAc)2H2O on refluxing[124] for 3 h with LH4 (57) in 1:3
molar ratio in the presence of the traces of AcOH forms an air-stable, dark-green, fivecoordinate, binuclear-dimeric, non-electrolyte (M = 1.4 mho cm2 mol-1 in DMSO),
[Cu4L2(H2O)4]4H2O. It decomposes at >300 oC. LH4 behaves as a tetrabasic hexadentate
ONOONO donor ligand. The compound shows a weak band at 16807 cm-1 due to the
{M2(2-O)2}grouping indicating the presence of naphthoxo-bridging in it. It shows a
shoulder at 18518 cm-1 indicating its square-pyramidal stereochemistry. In DMSO
solution, this band shifts to 18181 cm-1 with molar extinction coefficient () = 250 dm3
mol-1 cm-1. The position of the band together with in DMSO still favours the squarepyramidal stereochemistry of the compound. This indicates that although the solvent
molecules interact with the compound, the interactions are not sufficiently strong enough
to alter its gross stereochemistry. The compound exhibits three g1, g2 and g3 values equal to
2.65, 2.258 and 2.423 respectively at room temperature. The corresponding g values at
LNT are 2.89, 2.263 and 2.410 respectively.
Coordination compounds of zinc(II)

Zinc (Zn) also known as spelter is the first row transition, bluish-white, diamagnetic
element in Group 12 of the Periodic Table. Its atomic number, atomic weight and
electronic configurations are 30, 65.38 amu and [Ar] 3d104s2 respectively. Its common
oxidation state is +2. Zn+2 is an essential mineral of biological and public health
importance. Its deficiency causes growth retardation in children, delayed sexual
maturation, infection susceptibility and diarrhoea etc. Enzymes with a zinc atom in the
reactive center are widespread in biochemistry, such as alcohol dehydrogenase in human
beings. Consumption of excess zinc can cause ataxia, lethargy and copper deficiency. Zinc
possesses antioxidant properties, which protect against premature aging of the skin and
muscles of the body. It is essential trace element for all living organism. The ability of
71
Zn(II) ion to form the coordination compounds with a wide range of ligands has been
reported. These ligands are coordinated to Zn(II) ion in a monodentate, bidentate,
tridentate, tetradentate and polydentate fashion. We present here a brief survey of the
Chemistry of coordination compounds of Zn(II) ion.
A.

Popovic et al.[125] have synthesized a monomeric, four-coordinate compound,
[ZnX2(LH)2] (where LH = 137; R = CH2Ph, C6H4(4-Me), X = Cl, Br, I). Although LH is

potentially a monobasic bidentate ON donor ligand, but acts as a neutral monodentate O
donor (keto form) ligand. The Zn(II) is surrounded by two halogen atoms and two O (keto
form) atoms of the Schiff bases. The weak intermolecular H-bond of the CHCl type in
[ZnX2(LH)2] (when R = CH2Ph, X = Cl) joins the molecules into endless chains. The
compound, when R = C6H4(4-Me), X = Cl crystallizes as the one-to-one solvate with
EtOH. Its X-rays structural data show that LH (tautomeric keto form) is weakly bound to
Zn ion (1.95-2.00 ). A distorted tetrahedral geometry has been suggested for it. The
tetrahedral distortion is most pronounced in [ZnX2(LH)2] (when R = CH2Ph, X = I).
Kaczmarek et al.[126] have synthesized a monomeric, four-coordinate compound,
[ZnCl2(LH2)2] [where LH2 = 26; R = R'' = H, R' = OH, R''' = 4-Me(1,3-C6H4)] by a onestep metal-promoted reaction between salicylaldehyde and 4-methyl-1,3-phenylenediamine in the presence of ZnCl2 in 2:1:1 molar ratios in EtOH. Although LH2 is
potentially a dibasic tetradentate ONNO donor Schiff base, but functions as a neutral
monodentate ligand coordinating through its one phenolic O atom only.
B.

Upon refluxing an EtOH solution of ZnCl26H2O and LH (80) in 1:2 molar ratio
for 2 h, a four-coordinate, non-electrolyte, [ZnL2] is obtained[51]. LH acts as a monobasic

bidentate ON donor ligand. The antibacterial activity of the compound against S. aureus,
B. subtilis, E. coli and A. niger is higher than the ligand.
Maurya et al.[2] have reported the synthesis of a brown, monomeric, fourcoordinate, non-electrolyte (M = 8.6 mho cm2 mol-1), [ZnL2]H2O (here LH = 25; R = 3OMe, R' = OH, R'' = H). It decomposes at 265 oC. It is soluble in DMF and DMSO. The
lattice water molecule is lost between 90-141 oC. It shows (ZnO) and (ZnN)
72
vibrations at 515 and 405 cm-1 respectively. LH acts as a monobasic bidentate ON donor
ligand. A tetrahedral structure has been suggested for the compound.
The reaction of 2-aminophenol with Zn(II) ions in the presence of
4-benzyloxybenzaldehyde or but-2-enal in 1:1:1 molar ratios yields[4] the orange-yellow,
four-coordinate compound, [ZnL2] or light-yellow compound, [ZnL'2] respectively (where
LH and L'H = 28 and 29 respectively). [ZnL2] and [ZnL'2] melt at 155 and 180 oC
respectively. Both LH and L'H act as monobasic bidentate ON donor ligands. [ZnL2]
displays the (ZnO) and (ZnN) vibrations at 560 and 445 cm-1 respectively, while
[ZnL'2] displays these vibrations at 582 and 461 cm-1 respectively. They are more active
than 2-aminophenol against S. dysenteria, E. coli, P. aeruginosa, B. subtilis, S. lutea and
S. aureus.
An EtOH solution of Zn(OAc)22H2O and LH2 (30; R = H) in 1:2 molar ratio upon
refluxing in the presence of TEM produce[6] a red, non-electrolyte (M = 4.2 mho cm2
mol-1) compound, [Zn(LH)2], which decomposes at 284 oC. LH2 acts as a monobasic
bidentate ON donor ligand.
The synthesis of the dinuclear, non-electrolyte, four-coordinate compound, [Zn2L2]
(here LH2 = 87; R = H, 5,6-benzo) has been reported[58]. Both the compounds are feebly
soluble in DMF and dioxane. The IR data are indicative of the monobasic bidentate
(phenolic O and azomethine N atoms) donor nature of the ligand per metal ion. The (Zn
O) and the (ZnN) vibrations occur at 500, 340 and 505, 345 cm-1 respectively. A
dinuclear, tetrahedral structure (88; R = H, 5,6-benzo, M = Zn, A = nil) has been
suggested to them.
An EtOH solution of ZnCl26H2O upon refluxing with L (138; R = Me, Ph) in 1:2
molar ratio produces[127] a six-coordinate compound, [ZnL2]Cl2. They are air-stable, nonhygroscopic, soluble in H2O and common organic solvents. They are 1:2 electrolytes (M
= 120.1-124.7 mho cm2 mol-1) in DMF. L acts as a neutral bidentate ON donor ligand. The
(ZnO) and (ZnN) bands appear at 550 and 475 cm-1 respectively. The toxic effects
of the compounds, ligands and ZnCl2 on the growth of the green algae (chorella) indicates
that ZnCl2 is more toxic than the compounds and the ligand. The less toxic nature of L is
due to the presence of substituted groups in the quinazolone ring.
73
On refluxing an EtOH solution of ZnCl2 and an H2O/EtOH solution of NaLH (89)
in 1:1 and 1:2 molar ratios, air and moisture stable, intense coloured, amorphous sixcoordinate
compound,
[59]
respectively
[ZnCl(LH)(H2O)3]
and
[Zn(LH)2(H2O)2]
are
obtained
. They are soluble in H2O, DMF and DMSO. The carboxylato group is
coordinated in a monodentate mode. NaLH behaves as a monobasic bidentate ON donor

(carboxylic O and endocyclic N of -lactam ring) ligand. The presence of (ZnO)
stretch at 525 cm-1 and (ZnN) stretch at 410 cm-1 also indicates the bonding through O
and N atoms. The former compound shows antibacterial activities higher than the ligand
against E. coli, S. pyogenes, S. aureous and shows the same activity against K.
pneumoniae and P. aeruginosa. The latter compound shows antibacterial activities higher
than the ligand against K. pneumoniae, P. aeruginosa, S. pyogenes and shows the same
activity against S. aureous and E. coli. The six-coordinate structures, 90 (M = Zn) for
[ZnCl(LH)(H2O)3] and 91 (M = Zn) for [Zn(LH)2(H2O)2] have been assigned.
At pH = 6 An EtOH solution of ZnCl24H2O and LH2 (92) in 1:2 molar ratio on
refluxing for 1 h, produce[61] a six-coordinate, non-electrolyte (M = 10.7 mho cm2 mol-1
in Me2CO) compound, [Zn(LH)2(H2O)2]. The Schiff base acts as a monobasic bidentate
NN donor ligand. The (ZnN) vibrations occur at 440 cm-1.
Latheef et al.[128] have observed that on refluxing an EtOH solution of
Zn(OAc)22H2O and LH2 (52; R = (2-OH)C6H4CH, R' = N(CH2)6, X = S) in 1:2 molar
ratio, a yellow, four-coordinate compound, [Zn(LH)2] is obtained. LH2 acts as a
monobasic bidentate NS donor ligand. The phenolic O atom does not take part in
coordination. The compound crystallizes in a triclinic fashion with a = 10.339 , b =
11.094 , c = 13.027 , = 82.64o, = 82.66o, = 79.17o and Z = 2. A distorted
tetrahedral geometry has been assigned to it.
The synthesis of a four-coordinate, non-electrolyte, [Zn(LH)2] (where LH2 = 139)
has been reported[129]. Although LH2 is potentially a dibasic tridentate ONS donor ligand,
but behaves as a monobasic bidentate NS donor in the present compound. The latter
exhibits (ZnN) and (ZnS) vibrations at 470 and 330 cm-1 respectively.
An orange, four-coordinate, non-electrolyte, [ZnL2]3H2O (here LH = 52; R =
(C9H6N)CH, R' = NH2, X = Se) is obtained by stirring an aqueous solution of
Zn(OAc)22H2O and an EtOH solution of LH in 1:1 molar ratio for 1 h[130]. It is soluble in
74
DMSO. LH2 behaves as a monobasic bidentate NSe donor ligand. The coordination sites
are azomethine N and Se atoms.
C.

Kumar et al.[10] have reported the synthesis of a light-yellow, polystyrene-anchored
four-coordinate compound, [PSCH2LHZn(DMF)] (here PSCH2LH3 = 34). The PRC of

the compound is 55.9 and the MBC of PSCH2LH3 is 0.38 mmol of Zn per g of the ligand.
PSCH2LH3 behaves as a dibasic tridentate ONO donor ligand.
A yellow, four-coordinate, dinulear compound, [Zn2L(MeOH)2] (140) (here LH4 =
70; X = OH) is obtained by refluxing a MeOH solution of LH4 and Zn(NO3)26H2O in
1:2 molar ratio for 3 h[41]. It is partially soluble in DMF and DMSO. It melts above 280 oC.
The IR data are indicative of the bis(dibasic tridentate) ONO donor nature of LH4. The
(ZnO) and the (ZnN) vibrations occur at 594 and 512 cm-1 respectively.
A yellow, nano-crystalline, four-coordinate complex, [ZnL(H2O)]Cl has been
synthesized by refluxing a MeOH solution of ZnCl2xH2O and LH (97) in 1:1 molar ratio
for 2 h[66]. The complex is 1:1 electrolyte (M = 83 mho cm2 mol-1 in MeOH). It is soluble
in DMF and DMSO. The ligand behaves as a monobasic tridentate NON donor
coordinating through its azomethine N, carboxylato O and imidazole N atoms. The loss of
coordinated H2O molecule, Cl- ion (as HCl gas) and organic skeleton occur between 210268, 252-274 and 402-560 oC respectively. Finally ZnO is obtained as residue.
The bright-yellow, six-coordinate heterochelates, [ZnLL'(H2O)]H2O (where LH2 =
100; R = R'' = H, R' = OH, R''' = Me, 128; L' = ophen) have been synthesized by stirring a
MeOH solution of LH2, L' and an aqueous solution of ZnCl22H2O in 1:1:1 molar
ratios[116]. The heterochelates decompose at 246 and 210oC respectively. Their molar
conductances are 50.4 and 57.1 mho cm2 mol-1 respectively. LH2 behaves as a dibasic
tridentate ONO donor ligand. The former heterochelate exhibits higher antibacterial
activity against E. aerogene, S. aureus, E. coli, M. morganii, S. dysenteric, B. cereus and
B. megaterum than the ligand. A distorted octahedral structure (129; M = Zn, R = Me,
128) has been suggested for it.
A MeOH solution of Zn(OAc)22H2O on stirring with a MeOH solution of LH
(115)
gives a red
coloured,
hexagonal crystals of a trinuclear
compound,
[ZnLZn(OAc)4ZnL][89]. The IR data are indicative of the involvement of phenolic O,
75
azomethine N and py N atoms of LH towards coordination. The complex exhibits (ZnO)
and (ZnN) vibrations at 459 and 365 cm-1 respectively. The acetato group is coordinated
in a bidentate bridging coordination mode. The trinuclear complex is built up of two
mononuclear [ZnL] moieties which are linked through bridging acetato and phenolate
groups to the central Zn atom. The two terminal zinc ions are coordinated with LH along
with the bridging bidentate acetato groups to form an intermediate trigonal bipyramidalsquare pyramidal structure, while the central zinc ion resides on a center of symmetry and
is surrounded by four O atoms from four bridging bidentate acetato and two phenolic O
atoms resulting in slightly distorted octahedral geometry. The compound crystallizes in a
triclinic fashion with a = 7.923 , b = 10.828 , c = 19.419 , = 99.00o, = 95.22o, =
99.79.17o and Z = 2. Fluorescence spectrum of the complex shows broad emission band
indicating charge transfer nature of the transition. The fluorescence quantum yield of
[ZnLZn(OAc)4ZnL] is higher than the ligand.
An H2O/MeOH solution of ZnCl22H2O on refluxing with a MeOH solution of LH2
(116; R = R' = H) for h in the presence of AcONa forms[90] 1:1 dimeric, five-coordinate
compound, [ZnL(H2O)]2. The synthesis of monomeric, four-coordinate adduct, [ZnLA]
(here A = py or H2O) has also been reported. The compound and adducts are air-stable.
They are non-electrolytes in DMF. [ZnL(py)] is fairly soluble in CHCl3, dioxane, C6H6
and DMF. On the other hand, [ZnL(H2O)]2 is almost insoluble in CHCl3, MeOH, EtOH
and C6H6 indicating its dimeric or polymeric nature. The IR data indicate the dibasic
tridentate ONS donor nature of the ligand. The coordination sites in [ZnL(H2O)]2 are
completed by the ligand bridging through deprotonated phenolic O atom.
The complexation of yellow coloured benzothiazoline (LH2, 46A, 46B) with
Zn(II) ion proceeds with the rearrangement of benzothiazoline ring to form the
corresponding brown,
non-electrolyte, [Zn(LH)(OAc)][20]. The benzothiaoline in the
presence of Zn(II) ion rearranges to form Schiff base. The latter coordinates in keto form
as monobasic tridentate ONS donor. The appearance of azomethine proton at 8.93 ppm
is indicative of ring opening of benzothiazoline on complexation.
An EtOH solution of Zn(OAc)22H2O, LH2 (52; R = (2-OH)C6H4CH, R' =
N(CH2)6, X = S) and B or BB' (here B = py, -picoline, BB' = bipy, ophen) in 1:1:1 molar
ratios upon refluxing produce yellow, four-coordinate adducts, [ZnLB] and yellow-orange,
76
five-coordinate heterochelates, [ZnL(BB')]nH2O (n = 3.5 and 1 respectively)[128]. LH2 acts
as a dibasic tridentate ONS donor ligand.
An aqueous solution of Zn(OAc)22H2O reacts[22] with an EtOH solution of LH2
(48) in 1:2 molar ratio in N2 atmosphere and forms an air-stable, white coordination
compound, [Zn(LH)2]. It decomposes at 187 oC and is soluble in Me2CO, DMF and
DMSO. It is non-electrolyte (M = 10.6 mho cm2 mol-1 in DMSO and 3.6 mho cm2 mol-1
in Me2CO). The Schiff base acts as a monobasic tridentate ligand and coordinates to the
metal ions through the alcoholic O, azomethine N and thiolato S atoms. An octahedral
structure (49, M = Zn) has been suggested for it.
An air-stable, four-coordinate, non-electrolyte, [ZnCl(LH)] (where LH2 = 50; R =
OMe, R' = NH2) has been synthesized by stirring a MeOH solution of ZnCl2 and NaLH in
1:2 molar ratio for 8 h at room temperature[43]. It is soluble in DMF and DMSO and
slightly soluble in MeCN. The carboxylato group coordinates in a monodentate fashion.
LH2 behaves as a monobasic tridentate OOS donor ligand. The presence of (ZnS)
stretch at 300 cm-1 indicates the coordination through S atom of thiophene moiety. The
compound remains inactive towards E. faecalis, E. coli, S. sonnei, P. mirabilis and S.
enteritidis, while shows lesser bactericidal activity than LH2 against S. aureus. A
tetrahedral structure (51; R = OMe, R' = NH2, M = Zn, A = nil) has been assigned to it.
A six-coordinate compound, [Zn(LH)2]3H2O (where LH2 = penicillin) has been
synthesized by stirring an aqueous solution of ZnCl2 and sodium salt of LH2 in 1:1 molar
ratio for 1 h at room temperature[91]. LH2 behaves as a monobasic tridentate OOO donor
ligand. The carboxylato group is coordinated in a monodentate fashion. An octahedral
structure (117, M = Zn, x = 3) has been assigned to the compound.
D.

A yellow, four-coordinate, non-electrolyte (M = 7.6 mho cm2 mol-1), [ZnL]2H2O
has been synthesized by refluxing a mixture of an H2O/EtOH solution of Zn(OAc)22H2O

and a DMF solution of LH2 (26; R = 3-OMe, R' = OH, R'' = H, R''' = C2H4) in 1:1 molar
ratio for 4 h[2]. It decomposes above 360 oC, is soluble in DMF and DMSO. The IR data
are indicative of the dibasic tetradentate ONNO donor nature of LH2. The compound
shows (ZnO) and (ZnN) vibrations at 510 an 460 cm-1 respectively.
77
The four-coordinate compound, [ZnL] (here LH2 = 104) is obtained by refluxing a
MeOH solution of Zn(OAc)24H2O and LH2 (in CH2Cl2) in 1:1 molar ratio[74]. LH2
behaves as a dibasic tetradentate ONNO donor ligand. A tetrahedral geometry has been
assigned to the complex.
An air-stable, four-coordinate compound, [ZnL] (where LH2 = 55) is obtained by
refluxing a MeOH solution of Zn(OAc)22H2O and a CH2Cl2 solution of LH2 in 1:1 molar
MeOH, EtOH. The IR data are indicative of the dibasic tetradentate ONNO donor nature
of the ligand. A distorted tetrahedral structure has been suggested to the compound.
An EtOH solution of Zn(OAc)22H2O and LH2 (101) in 1:1 molar ratio on
refluxing for 3 h forms a four-coordinate, non-electrolyte (M = 14.21 mho cm2 mol-1 in
DMF), [ZnL]3H2O. It melts and decomposes at 278 and 295 oC respectively[70]. LH2 acts
as a dibasic tetradentate ONNO donor ligand.
Basak et al.[131] have synthesized light-yellow, five-coordinate, dinuclear, end-on
bridged compounds, [ZnL(1,1-AA)ZnL(AA)(H2O)x]yH2O [here LH = 133; R = H, R' =
(2-OH)(3-OMe)C6H3, R'' = (CH2)2NMe2], AA = N3, NCO, x = 0, y = 1; AA = NCS, x =
1, y = 0) by stirring a MeOH solution of Zn(OCOCCl3)2H2O, LH and AA. One ligand
behaves as a monobasic tetradentate OONN donor, while another as a monobasic
tridentate ONN donor with a non-bonded OMe group. One AA binds two metal centres in
an end-on bdidging mode and other as a terminal ligand. The loss of intramolecular Hbonded H2O molecules present in the crystal lattice takes place at 100-110 oC in [ZnL(1,1NCO)ZnL(NCO)]H2O. The compound, [ZnL(1,1-NCS)ZnL(NCS)(H2O)] loses the
coordinated H2O molecules between 168-178 oC. They crystallize in a monoclinic fashion
with a = 15.625 , b = 13.846 , c = 13.911 , = = 90o, = 105.2o and Z = 4 for
[ZnL(1,1N3)ZnL(N3)]1.5H2O; a = 15.763 , b = 13.719 , c = 13.983 , = = 90o,
= 105.29o and Z = 4 for [ZnL(1,1NCO)ZnL(NCO)]1.5H2O and a = 15.970 , b =
13.790 , c = 13.891 , = = 90o, = 103.32o and Z = 4 for [ZnL(1,1
NCS)ZnL(NCS)(H2O)] respectively.
An EtOH solution of Zn(OAc)24H2O and LH2 (105; R = H, Cl, Me) in equimolar
ratio on refluxing for 4 h produce four-coordinate, air-stable, non-hygroscopic, nonelectrolyte (M = 1.3-2.0 mho cm2 mol-1) complex, [ZnL][76]. The complexes are soluble in
78
DMSO. The ligand coordinates to the metal ion through its carboxylic O, ethereal O,
azomethine N and thione S atoms. The complexes exhibit (CS) stretch between 623650 cm-1. The carboxylic proton of LH2 occurring at 13.1 ppm gets disappeared in
complexes. The signal due to the 2NH hydrazinic proton occurring between 11.83-11.96
ppm is absent and the signal due to 4NH amine proton ( 9.99-10.11 ppm) is observed
upfield ( 9.20-9.43 ppm) in the complexes. A singlet at 8.57-8.59 ppm, due to
azomethine proton of the ligand suffers a small shift ( 8.81-8.86 ppm) and significant
decrease in intensity in the complexes. The coordination of ethereal O atom is supported
by the upfield shift and considerable decrease in intensity of the signal assigned to the
methylene protons of LH2 ( 4.80-4.81 ppm) and the complexes ( 4.57-4.59 ppm).
E.

Matesanz et al.[132] have claimed to be the first to synthesize a S-bridged dimeric
compound, [Zn(LH2)Br0.49(OH)0.51]2(HSO4)26H2O (here LH2 = 64; R = R' = H). The

ligand acts as a neutral pentadentate SNNNS donor ligand. In the compound, each zinc ion
is seven-coordinated with the SNNNS-chelating ligand occupying the five equatorial
positions, a bromine atom or hydroxo group in one of the two axial positions. The S atom
of the centro-symmetrical molecule occupies the other axial site making a bridge between
the two zinc ions.
Ali et al.[133] have synthesized an air-stable, crystalline, seven-coordinate,
monomeric compound, [Zn(NO3)2(LH2)] (here LH2 = neutral pentadentate SNNNS donor
ligand, 64; R = H, R' = Me) by refluxing Zn(NO3)26H2O and LH2 in 1:1 molar ratio. The
(C==N)(azomethine) and the (C==S) stretches of LH2 occurring at 1646 and 894 cm-1
shift to 1628 and 882 cm-1 respectively in the compound. The occurrence of bands at 1498
and 1308 cm-1 indicates the monodentate coordination mode of nitrato group. Each Zn(II)
ion is ligated to py N, two imine N and two thione S atoms of the ligand. The two axially
coordinated monodentate nitrato groups complete the seven-coordinate geometry. The
compound displays an additional S M charge transfer band at 22222 cm-1 lending
support for the coordinated mode of thione S atoms. A distorted pentagonal-bipyramidal
geometry has been suggested for it.
79
F.

An EtOH solution of Zn(OAc)22H2O on refluxing for 3 h with LH4 (57) in 1:3
molar ratio in the presence of the traces of AcOH forms[124] a dark-yellow, five-coordinate,
binuclear-dimeric compound, [Zn4 L2(H2O)4]4H2O. Another dark-yellow, five-coordinate,
binuclear-dimeric compound, K4[(ZnF)4L2]4H2O is obtained by refluxing an EtOH/H2O
suspension of [Zn4L2(H2O)4]4H2O and an aqueous solution of KF in 1:3 molar ratio for 3
h. They are insoluble in H2O, MeOH, EtOH, CCl4, CHCl3, C6H6, and Et2O. They are airstable and decompose >300 oC. The molar conductance value (M = 1.8 mho cm2 mol-1 in
DMSO) of [Zn4L2(H2O)4]4H2O indicates its non-electrolytic nature, on the other hand,
the value of M (57.4 mho cm2 mol-1 in DMSO) for K4[(ZnF)4L2]4H2O favours its ionic
nature. They lose four H2O molecules at 110 oC indicating the presence of the water of
lattice in them. LH4 behaves as a tetrabasic ligand. The charge-transfer band at ~22220
cm-1 is responsible for their dark-yellow colour. A square-pyramidal structure has been
suggested to them.
Ghosh et al.[134] have noticed that the air-stable, non-hygroscopic, dinuclear, fivecoordinate compounds, [Zn2X4L] and [Zn2X4L'] (here L = 141 and L' = 142; X = N3,
NCS) are obtained by mixing a MeOH solution of Zn(ClO4)26H2O and the corresponding
ligands in 2:1 molar ratio followed by adding an aqueous solution of NaN3/NH4NCS
respectively dropwise. On the other hand, by mixing a MeOH solution of L or L' and
Zn(NO3)24H2O and NaN3/NH4NCS in 1:2:4 molar ratios, the air-stable, non-hygroscopic,
1:1 electrolytic ion-pair coordination compounds, [ZnL][ZnX4] and [ZnL'][ZnX4] (here L
and L' = above Schiff bases; X = N3, NCS) are obtained. They are soluble in MeOH,
EtOH, MeCN, DMF and DMSO. L and L' act as the neutral hexadentate N6 donor ligands.
The dinuclear compound, [Zn2X4L'] (here L' = 142; X = N3) crystallizes in a triclinic
fashion with a = 7.91 , b = 9.14 , c = 9.63 , = 74.07o, = 83.50o, = 87.38o and Z =
1. A distorted trigonal-bipyramidal geometry has been suggested for it. In 1:1 electrolyte,
each Zn(II) ion has a distorted octahedral geometry in the cationic part and a distorted
tetrahedral in the anionic part. [ZnL][ZnX4] (here L = 141; X = NCS) crystallizes in a
monoclinic fashion with a = 9.79 , b = 15.66 , c = 19.19 , = = 90o, = 90.86o and
Z = 4.
80
Coordination compounds of zirconium:
Zirconium (Zr) is the second member of Group 4 and the second member of the
second transition series in the Periodic Table. It exhibits five oxidation states, i.e., 0, +1,
+2, +3 and +4. Out of these, +4 is the most stable oxidation state and has been studied
more extensively. In this oxidation state, zirconium may exist as oxozirconium(IV) cation,
[ZrO]2+ or dihydroxozirconium(IV) cation, [Zr(OH)2]2+. Syamal et al.[135] have developed
a non-aqueous titrimetric method to distinguish the compounds possessing the [ZrO]2+ or
[Zr(OH)2]2+ moiety. Oxozirconium(IV) compounds react with 3M HCl and as a result, the
oxo group gets protonated, while the zirconium(IV) compounds containing [Zr(OH)2]2+
group do not add up HCl at all. The infrared spectral studies have also been used to
differentiate between [ZrO]2+ and [Zr(OH)2]2+ moieties. The compounds containing the
[ZrO]2+ moiety have been reported to exhibit the (Zr==O) stretch[136-144] between 835-955
cm-1. The monomeric Zr(IV) compounds possessing [Zr(OH)2]2+ moiety[145-149] are known
to exhibit (ZrOH) bending between 1100-1150 cm-1. The ability of Zr(IV) ion to form
the coordination compounds with a wide range of ligands has been reported. These ligands
are coordinated to Zr(IV) ion in a monodentate, bidentate, tridentate, tetradentate and
polydentate fashion. We present here a brief survey of the Chemistry of coordination
compounds of Zr(IV) ion.
A.

An Me2CO solution of HDAOHTZC and LH (25; R = H, R' = OH, R'' = H, 4-Cl,
4-Me, 4-OMe) in 1:2 molar ratio[150] on refluxing produce five-coordinate compounds,

[ZrOCl2(LH)2]. Although, LH is a potential monobasic bidentate ON donor ligand, it
behaves as a neutral monodentate N donor ligand.
A dry C6H6 solution of BCPDZC, LH2 (25; R = H, R' = OH, R'' = 2-OH, SH) and
en in 1:1:1 molar ratios on refluxing form[145] [Cp2Zr(LH2)(en)]Cl2 (143; X = O, S). A dry
C6H6 solution of [Cp2Zr(LH2)]Cl2 (here LH2 = 25; R = H, R' = OH, R'' = 2-OH, SH ) on
refluxing with neutral monodentate N donor ligands (py or morpholine) in 1:2 molar ratio
also forms[145] [Cp2Zr(LH2)(py)2/(morp)2]Cl2, (144; X = O, S, morp = morpholine). The
coordination compounds are dark-brown, non-hygroscopic, high melting crystalline solids.
They are monomeric, 1:2 electrolyte (in PhNO2) and stable to aerial oxidation. The
azomethine N atom of LH2 is involved towards coordination. The (CO) and (C
81
S) stretches remain unaltered in the compounds. The data indicate the presence of
coordinated en, py or morpholine molecules. The (ZrN) vibrations occur at ~375 cm-1.
A square-pyramidal geometry has been assigned to them.
The syntheses of monomeric, non-electrolyte, eight-coordinate compounds,
[Zr(OH)2(NO3)2L2] and [Zr(OH)2X2L4] (here L = 145; R = R' = H, R'' = H, 4-NMe2, X =
Br, I, NCS) have been reported[151,152]. The compounds, except the iodine analogue, are
stable and storable at room temperature. The iodine analogue exhibits antifungal activity
and decomposes to sticky mass after a few weeks. They exhibit the (ZrN) vibrations
between 430-450 cm-1. The nitrato groups behave as the monobasic bidentate OO donor
ligands in [Zr(OH)2)(NO3)2L2].
B.

A
dark-brown,
monomeric,
six-coordinate,
non-electrolyte
(in
PhNO2),
[Cp2Zr(LH)2] (where LH2 = 131; R = 5-Me, R' = H, R'' = OH) and another light-brown,
monomeric, six-coordinate compound, [Cp2Zr(L'H)2] (here L'H2 = 133; R = PhCH(OH),
R' = Ph, R'' = OH) have been synthesized[153]. They are soluble in C6H6, THF, CHCl3 and
Me2CO. They are susceptible to hydrolysis and decompose on heating between 193-240
o
C. The IR data are indicative of the monobasic bidentate ON donor nature of LH2 and
L'H2. The (ZrO) and the (ZrN) frequencies occur between 530-570 cm-1 and 420520 cm-1 respectively.
Gupta et al.[154] have reported the syntheses of [(ZrOPri)4-xLx] (here LH = 25; R =
R' = H, R'' = 2-OH; R = H, R' = OH, R'' = H; R = 5,6-benzo, R' = OH, R'' = H) and 146 (R
= R' = H, R'' = (CH2)2, CH2CHMe, OPri = 2-propoxide, x = 1-4). LH acts as a monobasic
bidentate ON donor ligand. [Zr(OPri)4-xLx] is five-, six-, seven- and eight-coordinate,
when x = 1, 2, 3 and 4 respectively.
A MeOH solution of LH (25; R = H, 3-Me, 4-Me, 5-Me, 3-OMe, 5-Cl, R = OH,
R'' = H) reacts[155] with HDAOHTZC and forms monomeric, six-coordinate compounds,
[ZrCl2L2]. LH behaves as a monobasic bidentate ON donor ligand.
Uttamchandani et al.[156] have synthesized the pale-yellow to dark-yellow,
monomeric, non-electrolyte, five-coordinate [Zr(OPri)3L]; monomeric, non-electrolyte,
six-coordinate [Zr(OPri)2L2] (LH = 25; R = 5,6-benzo, R' = OH, R'' = 2-Me, 4-Me);
dimeric, non-electrolyte, six-coordinate [Zr(OPri)3L]2 (LH = 25; R = H, R' = OH, R'' = 2-
82
Me, 4-Me) and seven-coordinate [Zr(OPri)2L2]2 (LH = 25; R = H, R' = OH, R'' = 2-Me, 4Me) coordination compounds. They are susceptible to hydrolysis, soluble in C6H6, PriOH
and CHCl3. LH coordinates to Zr through its phenolic O and azomethine N atoms.
The four-coordinate compounds, [ZrOClL] (here LH = 25; R = H, R = OH, R =
2-Me, 3-Me, 2-OMe) have been synthesized[157]. LH behaves as a monobasic bidentate
ON donor ligand.
An Me2CO solution of HDAOHTZC or HDAOHTZITC reacts[149] with LH (25; R
= H, R' = OH, R'' = 2-Cl, 4-Me, 4-OMe) in 1:2 molar ratio and forms the tetrameric
compounds, [Zr4(OH)8(H2O)8(LH)4]Cl8 or [Zr4(OH)8(H2O)8(LH)4](NCS)8 respectively.
[Zr4(OH)8(H2O)8(LH)4]X8 is yellow (when LH = 25; R = H, R' = OH, R'' = 2-Me and 4OMe, X = Cl), brown (when LH = 25; R = H, R' = OH, R'' = 4-OMe, X = NCS) and brickred (when LH = 25; R = H, R' = OH, R'' = 2-Cl, X = Cl). They melt above 240 oC and are
insoluble in common organic solvents. LH acts as a neutral bidentate ON donor ligand.
The thiocyanato compound is more stable than the corresponding chloro compounds.
The synthesis of six-coordinat e compound, [ZrCl2L2] (here LH = 25; R = 3-Me,
R' = OH, R'' = 2,3,4,5,6-F5) has been reported by Lamberti et al.[158] LH behaves as a
monobasic bidentate ligand coordinating through its phenolic O and azomethine N atoms.
The X-rays structure of the compound indicates that it adopts a distorted octahedral
structure.
Although LH2 (25; R = H, R' = OH, R'' = 2-OH) is a potential dibasic tridentate
ONO donor ligand, it acts as a monobasic bidentate ON donor ligand[159] in fourcoordinate compound, [ZrOCl(LH)] and in five-coordinate compound, [ZrO(LH)2].
Kumar et al.[160] have synthesized a cream coloured, polystyrene-anchored sevencoordinate compound, [PSLZr(OH)2(OAc)(DMF)2] by refluxing a DMF swollen
suspension of polystyrene-anchored Schiff base, PSLH (obtained by the condensation of
aldehydopolystyrene and 2-aminophenol) and a DMF solution of freshly prepared
HDAOHTZAc in 1:2 molar ratio in ethyl acetate in the presence of TEA. The PRC of the
compound is 47.6 and the MBC of PSLH is 0.37 mmol of Zr per g of the ligand. PSLH
behaves as a monobasic bidentate ON donor ligand. The acetato group acts as a
monodentate ligand. DMF molecules are coordinated to Zr as indicated by the decrease of
(C==O) stretch of DMF from 1680 cm-1 to 1665 cm-1. The compound exhibits (Zr
83
OH) bending mode at 1115 cm-1. A pentagonal-bipyramidal structure has been suggested
to it.
Chako et al.[161] have synthesized a dimeric, six-coordinate compound,
[ZrCl2(LH)2]2 (where LH2 = 25; R = 3-OMe, R' = OH, R'' = 2-COOH). Although LH2 is a
potential dibasic tridentate ONO donor ligand, it behaves as a monobasic bidentate ON
donor ligand in the present case. The compound exhibits the (ZrO) and (ZrN)
vibrations at 510 and 410 cm-1 respectively.
Kumar et al.[162] have reported that a DMF swollen suspension of PSCH2LH2
(147) and a DMF solution of freshly prepared HDAOHTZAc in 1:2 molar ratio on
refluxing for 5 h produces a brown, seven-coordinate, polystyrene-anchored compound,
[PSCH2LHZr(OH)2 (OAc)(DMF)2]. The PRC of the compound is 30.3 and the MBC of
the ligand is 0.22 mmol of Zr per g of the ligand. The Schiff base acts as a monobasic
bidentate ON donor ligand. The acetato ligand coordinates in a monodentate fashion. The
compound exhibits (ZrOH) bending vibrations at 1110 cm-1. A pentagonal-bipyramidal
structure has been suggested to it.
The coordination compound formation between Zr and LH2, 52[R = (2OH)C6H4CH, R' = H, X = O] has been studied fluorometrically in aq. solution[163]. They
are most stable at pH = 2.
Srivastava et al.[164] have reported the syntheses of the five-coordinate
[Cp2ZrCl(LH)] and six-coordinate, compounds, [Cp2ZrCl2(LH2)] (where LH2 = 148, R =
Ph, 2-ClC6H4,
3-NO2C6H4, 4-MeC6H4). The IR data indicate the neutral bidentate
(ketonic O and azomethine N) and the monobasic bidentate (enolic O and azomethine N)
donor nature of LH2 in [Cp2ZrCl2(LH2)] and [Cp2ZrCl(LH)] respectively. The (Zr
O)(enolic), (ZrO)(ketonic), (ZrN) and (ZrCl) frequencies occur at 480-500,
440-465, 350-360 and 260-275 cm-1 respectively.
El-Tabl
et
al.[8]
have
synthesized
red,
five-coordinate
compound,
[ZrOCl2(LH2)]8H2O (where LH2 = 32) by refluxing an EtOH solution of LH2 and

HDAOHTZC in 1:1 molar ratio. It is insoluble in H2O, EtOH, C6H6 and C6H5Me, partly
soluble in MeCN and CHCl3, but completely soluble in DMF and DMSO. It is nonelecrolyte (M = 4.0 mho cm2 mol-1) and melts at 280 oC. It is stable at room temperature
and does not decompose even after prolonged storage. LH2 acts as a neutral bidentate ON
84
donor ligand. The (ZrO), (ZrN) and (ZrCl) frequencies occur at 640, 553 and
350 cm-1 respectively.
Raman et al.[165] have synthesized a monomeric, five-coordinate, non-electrolyte
(M = 0.9 mho cm2 mol-1) compound, [ZrOL2] (where LH = Schiff base obtained from the
condensation of acetoacetanilide and 4-aminoantipyrine) by reacting an EtOH solution of
HDAOHTZC and LH in 1:2 molar ratio for 3 h in the presence of 5% aq. AcONa solution.
The antimicrobial activities against S. aureus, B. subtilis, K. pneumoniae, E. coli, C.
ferundii and S. typhi indicate that [ZrOL2] exhibits better antimicrobial activity than LH.
Although LH4 (149; R = H, 5-Cl, 5-Me, 5-OMe and 5,6-benzo, X = S) is a
potential dibasic haptadentate ONNSNNO donor ligand, it acts[166] as a monobasic
bidentate ON donor ligand in [ZrO(LH3)2]. The compounds are five-coordinate, nonelectrolytes and soluble in DMF, DMSO and pyridine. LH4 coordinates to Zr through one
each of the phenolic O and azomethine N atoms. The (ZrO) and (ZrN) vibrations
occur between 470-560 and 350-420 cm-1 respectively.
Relatively little work has been reported on Zr(IV) coordination compounds with
bidentate Schiff bases containing S donor atom. The compounds possessing the S donor
ligands such as thiosemicarbazones, dithiocarbazates and benzothiazolines are known for
their spectacular progress in coordination and bio-inorganic chemistry[167]. The study of
coordination compounds of Schiff bases containing S atom is of biochemical interest due
to their carcinostatic (anticancer)[168], antibacterial[169] and antifungal activities[170]. S
donor compounds are known to be the most effective anticancer agents as they usually
confer lipid solubility on them. S donor Schiff bases have also been used as PVC
stabilizer[171], agrochemicals and antifouling paints due to their low photo-toxicity and
favourable environmental degradation[172].
The syntheses of [ZrCl4(LH)n] [where LH = 52; R = C6H5CH, R' = NH2, X = S, n =
1, 2] and [ZrCl4(L'H)n] [here L'H = 52; R = C6H11CH, R' = S-Me, n = 1, 2, 4] have been
reported[173,174]. One LH acts as a solvate molecule in [ZrCl4(LH)n]. The third and fourth
L'H molecules are H-bonded and are not coordinated in [ZrCl4(L'H)n]. LH and L'H act as a
neutral bidentate NS donor ligand.
The yellow to brown, five-coordinate [Cp2ZrClL] and the brown, six-coordinate
compounds, [CpZrClL2] (where LH = 150; R = Me, R' = Me, Et, 1-Pr) have been
85
synthesized under anhydrous conditions and inert atmosphere[175]. They are air-stable but
their solutions undergo hydrolysis on standing for a long period. They are non-electrolytes
in PhNO2. LH acts as a monobasic bidentate NS donor ligand. The (ZrN) and the (Zr
S) vibrations occur between 450-470 and 370-390 cm-1 respectively.
Sengupta et al.[176] have synthesized brown, thermally-stable, non-electrolytes,
five-coordinate, [Cp2ZrClL] and another dark-brown, seven-coordinate, [CpZrL3] (where
LH = 151; R = H, 2-Cl, 4-OMe, R' = R'' = H, X = S). They decompose above 150 oC
without melting. LH behaves as a monobasic bidentate NS donor ligand. The (ZrN)
and (ZS) vibrations occur between 430-460 and 335-360 cm-1 respectively.
C.

Syamal et al.[177] have synthesized monomeric, seven-coordinate oxozirconium(IV)
compounds, [ZrO(LH)2] [where LH2 = 131; R = H, 5-Cl, 5-Br, 5-NO2, 3-OMe, 4-OMe, 5OMe, 3-OEt, 3,5-Cl2, 5,6-benzo, R' = H, R'' = (CH2)2OH]. They are non-electrolytes (M
= 2.5-9.7 mho cm2 mol-1) in MeOH. LH2 acts as a monobasic tridentate ONO donor
ligand.
A
yellowish-brown,
polystyrene-anchored,
seven-coordinate
compound,
[PSCH2LZr(OH)2(DMF)2] (where PSCH2LH2 = 152; R = R' = H, R'' = COOCH2PS, X

= O, n = 1) has been synthesized[7]. The PRC of the compound is 92.6 and the MBC of the
ligand is 0.71 mmol of Zr per g of it. The compound exhibits the (ZrOH) bending
mode at 1118 cm-1. A pentagonal-bipyramidal structure has been suggested for it.
Kumar et al.[10] have synthesized a cream, polystyrene-anchored seven-coordinate
compound, [PSCH2LHZr(OH)2(DMF)2] (where PSCH2LH3 = 34) by refluxing a DMF
swollen suspension of
PSCH2LH3 and a DMF solution of freshly prepared
HDAOHTZAc . The PRC of the compound is 40.3 and the MBC of PSCH2LH3 is 0.25
mmol of Zr per g of the ligand. 34 behaves as a dibasic tridentate ONO donor ligand.
DMF molecules are coordinated to Zr as indicated by the decrease of (C==O) stretch of
DMF from 1680 cm-1 to 1650 cm-1. The compound exhibits (ZrOH) bending mode at
1140 cm-1. A pentagonal-bipyramidal structure has been suggested to it.
Sharma et al.[178] have synthesized the yellow to yellowish-brown, monomeric (in
boiling C6H6 or CHCl3), six-coordinate, mixed Schiff base heterochelates, [ZrLL'] [where
LH2 = 146; R = H, R' = OH, R'' = (CH2)2; L'H2 = 146 [R = 5,6-benzo, R' = OH, R'' =
86
(CH2)2, (CH2)3], 152 (R = R'' = H, R' = Me, X = O, n = 1, 2] and 130 [R = R' = Me, R'' =
(CH2)2OH, (CH2)3OH, CH2CHMeOH, CH2CHMeCH2OH and C6H4(2-OH)] by refluxing
a C6H6 solution of TKPZP, LH2 and L'H2 in 1:1:1 molar ratios. LH2 and L'H2 behave as the
dibasic tridentate ONO donor ligands. The heterochelates exhibit the (ZrO) vibrations
between 520-640 cm-1.
A MeOH or Me2CO solution of TKACACZ and LH2 (152; R = R' = R'' = H, X =
O, n = 1) in 1:2 molar ratio on refluxing[179] produces a yellow-white, seven-coordinate,
non-electrolyte, heterochelate, [ZrL(acac)2]. It is sparingly soluble in common organic
solvents and gets decomposed above 250 oC. The IR data indicate a dibasic tridentate
ONO donor nature of LH2 and a monobasic bidentate OO donor nature of acacH. On
prolonged heating at 120 oC, [ZrL(acac)2] loses acacH completely.
Syamal et al.[180] have synthesized monomeric, seven-coordinate compounds,
[ZrO(LH)2] [where LH2 = 146; R = H, 5-Cl, 5-Br, 5-NO2, 3-OEt, 3-OMe, 4-OMe, 5-OMe
3,5-Cl2, 5,6-benzo, R' = OH, R'' = (CH2)3, (CH2)4]. LH2 behaves as a dibasic tridentate
ONO donor ligand.
Biradar et al.[181] have synthesized yellowish-brown, non-electrolytes (M = ~35
mho cm2 mol-1 in DMF), six-coordinate, oxo-bridged compounds, [Zr2OCl2L3] (where
LH2 = 25; R = H, 3-OMe, 3-Me, 4-Me, 5-Me, 5-Cl, R' = OH, R" = 2-OH) by refluxing a
MeOH solution of HDAOHTZC and LH2 in 1:2 molar ratio for 3-4 h. The Schiff base
behaves as a tridentate ONO donor ligand.The (ZrOZr) stretch occurs at ~848 cm-1.
Eight-coordinate compounds, [Zr(OH)2(LH)2] (here LH2 = 25; R = H, 5-Cl, 5-Br,
5-NO2, 5,6-benzo, R' = OH, R'' = 2-OH) are obtained on refluxing a MeOH solution of
freshly prepared HDAOHTZAc and LH2 in 1:2 molar ratio[182]. However, in the presence
of MeONa, a MeOH solution of freshly prepared HDAOHTZAc and LH2 in 1:1 molar
ratio on refluxing forms the seven-coordinate compounds, [Zr(OH)2L(MeOH)2]. They are
monomers (in diphenyl) and non-electrolytes (0.2-1.9 mho cm2 mol-1 in THF). They
exhibit the (ZrOH) bending mode between 1100-1135 cm-1. MeOH is coordinated to
Zr in [Zr(OH)2L(MeOH)2]. LH2 acts as a monobasic tridentate ONO donor in
[Zr(OH)2(LH)2] and as a dibasic tridentate ONO donor in [Zr(OH)2L(MeOH)2].
Gupta et al.[183] have synthesized brown, five-coordinate [Zr(OPri)2L] and sixcoordinate [ZrL2] compounds by refluxing TKPZP and LH2 (25; R = H, R' = OH, R" =
87
2-OH) or 130 [R = R' = Me, R" = C6H4(2-OH); R = Me, R' = Ph, R" = C6H4(2-OH)] in 1:1
and 1:2 molar ratios respectively. LH2 acts as a dibasic tridentate ONO donor ligand.
A
dark-brown,
non-hygroscopic,
high
melting
crystalline
solid,
N-(2-
hydroxyphenyl)-salicylideneiminebis(cyclopentadienyl)zirconium(IV)chloride,
[Cp2Zr(LH2)]Cl2 (153, X = O) (here LH2 = 25; R = H, R' = OH, R" = 2-OH) has been
synthesized by refluxing a dry C6H6 solution of BCPDZC and LH2 in 1:1 molar ratio for 6
h[145]. It decomposes at 225 oC. It reacts with Cl(CH2)2Cl in 1:1 molar ratio in dry C6H6 in
the
presence
of
NaOH
to
form
dibenzo-1-aza-4,7-peroxocyclodeca-1-
enebis(cyclopentadienyl)zirconium(IV) chloride (154, X = O). They are stable to aerial

oxidation and are 1:2 electrolytes in PhNO2. The phenolic O and azomethine N atoms of
LH2 are involved towards coordination indicating its dibasic tridentate ONO behaviour.
The (ZrO) and the (ZrN) vibrations occur at 390 and 375 cm-1 respectively. The
square-pyramidal structures (153 and 154) have been assigned to them.
The
synthesis
of a
seven-coordinate,
coordination
compound, [PSCH2LZr(OH)2(DMF)2] (where PSCH2LH2 = 155; X = Y = nil, R = 3PSCH2OCO) has been reported[184]. The PRC of the compound is 76.0 and the MBC of the
ligand is 0.57 mmol of Zr per g of it. The Schiff base acts as a dibasic tridentate ONO
donor ligand. The compound exhibits (ZrOH) bending mode at 1115 cm-1. A
pentagonal-bipyramidal structure has been suggested for it.
The synthesis of a cream coloured, seven-coordinate, polystyrene-anchored
compound, [PSCH2LZr(OH)2(DMSO)2] (where PSCH2LH2 = 156, R = H) has been
reported[185]. The PRC of the compound is 28.0 and the MBC of the ligand is 0.19 mmol
of Zr per g of it. The compound exhibits the (ZrOH) bending mode at 1148 cm-1. A
pentagonal-bipyramidal structure has been suggested to it.
Syamal et al.[186] have synthesized yellow, monomeric, eight-coordinate, nonelectrolytes (M = 3-5 mho cm2 mol-1 in MeOH) [Zr(OH)2(LH)2] (where LH2 = 155; R =
H, 5-Cl, 5-Br, 5-NO2, 5-OMe, 3-OEt, 3,5-Cl2, X = CH2, Y = nil). LH2 behaves as a
monobasic tridentate ONO donor.
The synthesis of a cream-coloured, seven-coordinate, polystyrene-anchored
compound, [PSCH2LZr(OH)2(DMF)2] (where PSCH2LH2 = 155; R = 3-PSCH2OCO, X
= CH2, Y = nil) has been reported[187]. The PRC of the compound is 99.0 and the MBC of
88
the ligand is 0.75 mmol of Zr per g of it. The compound exhibits the (ZrOH) bending
mode at 1100 cm-1. A pentagonal-bipyramidal structure has been suggested to it.
Syamal et al.[188] have reported the synthesis of a seven-coordinate, polystyreneanchored compound, [PSCH2LZr(OH)2(DMF)2] (where PSCH2LH2 = 155; R = 3PSCH2OCO, X = nil, Y = CH2). The PRC of the compound is 92.0 and the MBC of
PSCH2LH2 is 0.685 mmol of Zr g-1 of it. The compound exhibits the (ZrOH) bending
mode at 1100 cm-1. A pentagonal-bipyramidal structure has been suggested to it.
The coordinating ability of LH2 (25; R = H, R' = OH, R'' = 2-COOH) with Zr(IV)
ions at different pH has been examined independently by two research teams[188,189].
Mahmoud et al.[189] have found that when an EtOH-H2O solution of Zr(NO3)44H2O is
refluxed with an EtOH solution of LH2 in 1:1 molar ratio, a resinous substance is obtained
by evaporating the excess of solvent, which upon trituration successively with ether gives
a six-coordinate compound, [ZrL(H2O)3](NO3)2. LH2 behaves as a dibasic tridentate ONO
donor ligand. The three bonding sites are the carboxylic O, phenolic O and azomethine N
atoms.
The alkaline solution of LH2 (25; R = H, 5-Cl, 5-Br, R' = OH, R" = 2-COOH)
reacts[190] with hot aq. solution of Zr(NO3)44H2O in 1:1 molar ratio in the pH range 3.54.5 using acetate buffer ions and forms yellow, monomeric, six-coordinate, nonelectrolytes (M = 0.42-0.80 mho cm2 mol-1 in PhNO2), [Zr(OH)2L(H2O)]. They are
soluble in DMF, PhNO2, stable against light and atmosphere. They decompose between
120-190 oC. LH2 behaves as a dibasic tridentate ONO donor ligand. The (ZrO) and
(ZrN) vibrations occur between 600-625 and 480-515 cm-1 respectively. The
coordinated water molecule is lost at 140 oC and form [Zr(OH)2L] is obtained.
Rabia et al.[191] have noticed that an EtOH-H2O solution of ZrCl4 on adding
dropwise to an EtOH-H2O solution of LH2 (96; R = 5,6-benzo, R' = OH, R'' = H, R''' = H,
Me, CH2Ph, CHMe2, CH2CHMe2) in 1:1 molar ratio in the presence of AcONa followed
by refluxing for 2 h at 70 oC forms yellow to pale-green, monomeric compounds,
[Zr(OAc)2L(H2O)] (when R''' = H, CHMe2), [Zr(OAc)2L(H2O)]H2O (when R''' = Me),
[ZrCl(OAc)L(H2O)] (when R''' = CH2Ph) and [Zr(OAc)2L] (when R''' = CH2CHMe2).
They are air-stable, decompose above 300 oC, sparingly soluble in H2O and fairly soluble
in DMF or DMSO. They are non-electrolytes (M = 5.3-15.4 mho cm2 mol-1) in DMF. The
89
acetato group acts as a bidentate ligand. The (ZrO) and (ZrN) vibrations occur
between 455-491 and 407-420 cm-1 respectively. Zr attains a coordination number of
seven
in
[ZrCl(OAc)L(H2O)],
[Zr(OAc)2L]
and
eight
in
[Zr(OAc)2L(H2O)],
[Zr(OAc)2L(H2O)]H2O.
Owing to the presence of carboxylic acid groups on both the starting materials i.e.,
3-formylsalicylic acid (3-Fsal) and glycine (gly) and to avoid the ester formation on both
aldehyde and glycine moieties, Kumar et al.[192] have developed an alternate method to
synthesize the polystyrene-anchored Schiff base, PSCH2LH2 (96; R = 3-PSCH2OCO, R'
= OH, R'' = R''' = H). A MeOH solution of freshly prepared HDAOHTZAc and a DMF
swollen suspension of PSCH2LH2 in 2:1 molar ratio on refluxing for 4 h forms a cream
coloured, polystyrene-anchored seven-coordinate compound, [PSCH2LZr(OH)2(DMF)2].
The PRC of the ligand is 81.89 and the MBC of the former is 0.63 mmol of Zr per g of it.
The compound exhibits (ZrOH) bending mode at 1115 cm-1.
Syamal and Kumar[193] have synthesized monomeric coordination compounds of
two different types, [Zr(OH)2(LH)2] and [Zr(OH)2L(MeOH)2] (here LH2 = 157; R = H, 5Cl, 5-Br, 5-NO2, 3-OMe, 3-OEt, 3,5-Cl2, 5, 6-benzo, R' = H, R'' = C6H5) under different
reaction conditions. They are non-electrolytes (M = 1-8 mho cm2 mol-1) in MeOH. They
exhibit (ZrOH) bending mode between 1100-1135 cm-1. LH2 acts as a monobasic
tridentate ONO donor ligand in [Zr(OH)2(LH)2] and as a dibasic tridentate ONO donor
ligand in [Zr(OH)2L(MeOH)2].
Dua et al.[194] have reported the syntheses of tetrameric, eight-coordinate, nonelectrolyte (in DMF and DMSO), [Zr(OH)2L(H2O)]4 (158; R = H, R' = H, Me, Et; R = 5,6benzo, R' = H) (here LH2 = 157; R = H, R' = H, Me, Et, R'' = C6H5; R = 5,6-benzo, R' = H,
R'' = C6H5). They are soluble in DMF, DMSO and CHCl3, partially soluble in Me2CO and
EtOH. The IR data show the dibasic tridentate ONO donor nature of LH2. The (ZrO),
(ZrN) and (ZrO)(enolic) stretches occur between 510-535, 460-485 and 415-435
cm-1 respectively.
Syamal and Kumar[195] have become the first to synthesize the Zr(IV)
heterochealtes containing a tridentate ONO donor Schiff base and a bidentate NN
donor ligand. The monomeric, seven-coordinate heterochelates, [Zr(OH)2L(AA)] (where
LH2 = 157; R = R' = H, R'' = Ph) have been synthesized by refluxing a MeOH solution of
90
freshly prepared solution of HDAOHTZAc, LH2 and NN donor bidentate ligand (AA = en,
pn, bn, phen, bipy, ophen) in equimolar ratio. These heterochelates are formed by the
replacement of two coordinated MeOH molecules from [Zr(OH)2L(MeOH)2] which is
formed in situ with a molecule of AA. The heterochelates are non-electrolytes (M = 1.35.6 mho cm2 mol-1) in MeOH. LH2 acts as a dibasic tridentate ONO donor ligand. The
(C==N)(ring) stretch of bipy (1582 cm-1) and ophen (1585 cm-1) shifts to higher energy
by 28 and 42 cm-1 respectively in the heterochelates. The (NH2) vibration of the aliphatic
and aromatic amines occurring at ~1620 cm-1 shifts to lower energy by 10-25 cm-1. The
heterochelates exhibit (ZrOH) bending mode between 1100-1130 cm-1. A pentagonalbipyramidal structure has been suggested for the heterochelates.
A DMF swollen suspension of PSCH2LH2 (157; R = 3-PSCH2OCO, R' = H, R'' =
C6H5) and a DMF solution of HDAOHTZAc in 1:2 molar ratio on refluxing for 6 h
form[196]
cream
coloured,
seven-coordinate,
compound,
[PSCH2LZr(OH)2(DMF)2]. Its PRC is 74.5 and the MBC of the ligand is 0.47 mmol of
Zr per g of it. PSCH2LH2 acts as a dibasic tridentate ONO donor. The (ZrOH)
bending mode occur at 1120 cm-1. A pentagonal-bipyramidal structure has been suggested
to it.
On refluxing a MeOH solution of freshly prepared HDAOHTZAc and LH3 [157; R
= H, 5-Cl, 5-Br, 5-NO2, 3-OEt, 5-OMe, 3,5-Cl2, 5,6-benzo, R' = H, R'' = 2-(OH)C6H4] for
4 h, the yellow, monomeric, non-electrolytes (1.9-7.7 mho cm2 mol-1), seven-coordinate,
oxozirconium(IV) compounds, [ZrO(LH2)2] are obtained[197]. LH3 acts as a monobasic
tridentate ONO donor ligand. Out of two phenolic OH groups in LH3, the phenolic O atom
of aldehyde moiety is coordinated.
Syamal and his team[135] have observed that on refluxing a MeOH solution of
freshly prepared HDAOHTZAc and LH2 (33; R = H, X = O) in 1:2 molar ratio, a yellow,
monomeric, eight-coordinate compound, [Zr(OH)2(LH)2] is obtained. On the other hand,
by refluxing a MeOH solution of freshly prepared HDAOHTZAc, LH2 and MeONa in
1:1:2
molar
ratios,
another
yellow,
monomeric,
seven-coordinate
compound,
[Zr(OH)2L(MeOH)2] is obtained. They are non-electrolytes and soluble in MeOH, EtOH,

DMF and DMSO. [Zr(OH)2L(MeOH)2] does not lose MeOH on heating at 110 oC
indicating the presence of coordinated MeOH molecules in it. LH2 acts as a monobasic
91
tridentate ONO donor ligand in [Zr(OH)2(LH)2], while as a dibasic tridentate ONO donor
ligand in [Zr(OH)2L(MeOH)2].
A DMF solution of freshly prepared HDAOHTZAc and a DMF swollen
suspension of PSCH2LH2 (33; R = 3-PSCH2OCO, X = O) in 2:1 molar ratio on
refluxing[9] for 6 h produces a seven-coordinate compound, [PSCH2LZr(OH)2(DMF)2].
Its PRC is 85.7 and the MBC of the ligand is 0.54 mmol of Zr per g of it. The Schiff base
behaves as a dibasic tridentate ONO donor ligand. The (ZrOH) bending mode occurs
at 1140 cm-1. A pentagonal-bipyramidal structure has been suggested for the compound.
Syamal et al.[198] have synthesized monomeric, eight-coordinate compounds,
[Zr(OH)2(LH)2] (where LH2 = 152; R = H, 5-Cl, 5-Br, 5-NO2, 4-OMe, 5,6-benzo, R' = R''
= H, X = S, n = 1) at room temperature by an alternate method. A MeOH solution of
freshly prepared HDAOHTZAc upon stirring with a MeOH solution of 2aminoethanethiol in 1:2 molar ratio, followed by the addition of a MeOH solution of R-sal
(R = H, 5-Cl, 5-Br, 5-NO2, 4-OMe, 5,6-benzo) gives yellow compounds. They are nonelectrolytes (M = 3-8 mho cm2 mol-1) in DMSO. The Schiff bases behave as dibasic
tridentate ONS donor ligands. The compounds exhibit (ZrOH) bending mode between
1100-1135 cm-1.
Tarafder et al.[199] have reported the synthesis of a yellow, six-coordinate, nonelectrolyte (M = 9.0 mho cm2 mol-1 in DMSO), [ZrOL(H2O)2] [here LH2 = 52; R = (2OH)C6H4CH, R' = SCH2Ph, X = S]. LH2 behaves as a dibasic tridentate ONS donor ligand
coordinating through its phenolic O, azomethine N and thiocarbazate S atoms. The Schiff
base and the compound are strongly active against P. aeruginosa. The Schiff base is active
against leukemic cells however, the compound is inactive.
A MeOH solution of freshly prepared HDAOHTZAc reacts with LH2 (25; R = H,
5-Cl, 5-Br, 5-NO2, 5,6- benzo, R' = OH, R'' = 3-SH) in 1:1 molar ratio in the presence of
MeONa
and
forms[200]
yellow,
dimeric,
seven-coordinate
compounds,
[Zr(OH)2L(MeOH)]2 (159; R = H, 5-Cl, 5-Br, 5-NO2, 5,6-benzo). They do not lose weight
on heating at 120 oC for 2 h indicaing that MeOH molecules are not lost at this
temperature and are coordinated to Zr. They are non-electrolytes (M = 0.71-3.85 mho cm2
mol-1) in MeOH. The (ZrOH) bending mode occurs between 1135-1145 cm-1. The di-hydroxo linkage[147] possessed by the starting material, HDAOHTZC is also retained by
92
the present compounds. The meta location of the thiol group sterically prohibits the
binding of it and the azomethine N to the same Zr atom. A pentagonal-bipyramidal,
dimetallic structure (159; R = H, 5-Cl, 5-Br, 5-NO2, 5,6- benzo) has been suggested for the
compound where O and N atoms of LH2 are chelated to one Zr atom and its S atom is
coordinated to another Zr atom.
A DMF swollen suspension of PSCH2LH2 (127; R = 3-PSCH2OCO, R' = OH, R''
= Me) on refluxing for 6 h with a DMF solution of HDAOHTZAc in 1:2 molar ratio
produces[201] a seven-coordinate, polystyrene-anchored compound, [PSCH2LZr(OH)2L
(MeOH)2]. The PRC of the compound is 63.9 and the MBC of the ligand is 0.41 mmol of
metal per g of it. PSCH2LH2 acts as a dibasic tridentate ONS donor ligand. A pentagonalbipyramidal structure has been suggested for it.
D.

The monomeric, eight-coordinate compound, [Zr(LH)2] (where LH3 = 160) is
obtained by refluxing an EtOH solution of [Zr(OBut)4] and LH3 in 1:2 molar ratio[146]. LH3
acts as a dibasic tetradentate ONNO donor ligand. The phenolic group present on the
methanediaminato moiety does not take part in coordination. The compound crystallizes in
a monoclinic fashion.
Biradar et al.[202] have synthesized [ZrCI2L] by refluxing a MeOH solution of
HDAOHTZC and LH2 [26; R = H, R' = OH, R'' = (CH2)2, (CH2)3] in 1:1 molar ratio for 2
h. They are non-electrolytes in DMF. LH2 behaves as a dibasic tetradentate ONNO donor
ligand. Being sterically favourable, LH2 encompasses Zr4+ ion in a cis-configuration, 161.
The two chlorine atoms occupy the trans-positions of the octahedron.
Gupta and Tandon[183] have synthesized six-coordinate [Zr(OPri)2L], [Zr(OPri)2L']
and eight-coordinate [ZrL2], [ZrL'2] [where LH2 = 26; R = R'' = H, R' = OH, R''' = (CH2)2;
L'H2 = 162; R = R' = Me; R = Me, R' = Ph; R'' = (CH2)2, X = O]. LH2 as well as L'H2
behave as the dibasic tetradentate ONNO donor ligands coordinating through both
azomethine N atoms and phenolic/enolic O atoms.
Corazza et al.[203] have synthesized a yellow, seven-coordinate compound,
[ZrCl2L(THF)] [here LH2 = 26; R = H, R' = OH, R'' = H, Me, R''' = (CH2)2] by refluxing a
THF solution of [ZrCl4(THF)2] and disodium salt of LH2 in 1:1 molar ratio under inert
atmosphere. If the above ratio is made > 1:1, overall replacement of Cl ligands takes place
93
and [ZrL2] is obtained. It is fairly soluble in organic solvents and is very sensitive to
moisture forming oxo compound. The IR data are indicative of the dibasic tetradentate
ONNO donor nature of LH2. The central metal ion is seven-coordinate with a pseudopentagonal-bipyramidal geometry. The equatorial plane of the bipyramid is formed by
N2O2 donor atoms and by the O atom of THF, while both the chloro ligands are trans- to
each other.
The catalytic activity of [ZrCl2L(THF)] [here LH2 = 26; R = H, R' = OH, R'' = H,
Me, R''' = (CH2)2] towards hexa-1,5-diene in the presence of activated methylalumoxane
(MAO) has been reported[204]. Methylenecyclopentane is the main product of the catalytic
cycle.
Repo et al.[205] have synthesized the seven-coordinate compound, [ZrCl2L(THF)]
[where LH2 = 26; R = R'' = H, R' = OH, R''' = (CH2)2]. The ligand occupies four sites in the
pseudopentagonal-bipyramidal coordination. The coordination sphere is completed by one
THF molecule and two chloro groups are forced into the trans-position.
The eight-coordinate compounds, [ZrL2] [where LH2 = 26; R = H, 3-Me, 4-Me, 5Me, 5-Cl, R' = OH, R'' = H, R''' = (CH2)2] have been reported[206]. LH2 behaves as a dibasic
tetradentate ONNO donor ligand.
Ghose et al.[207] have synthesized five-coordinate compounds, [ZrOL] [where LH2
= 26; R = H, R' = OH, R'' = H, Me, R''' = (CH2)n (n = 2-4); R = OMe, R' = OH, R'' = H, R'''
= (CH2)2]. LH2 acts as the dibasic tetradentate ONNO donor ligand.
Mishra et al.[179] have become the first to synthesize the mixed Schiff base
coordination compounds possessing a tri- and a tetradentate Schiff base together. On
adding a MeOH solution of TKACACZ to a constantly stirred MeOH solution of LH2 [26;
R = R'' = H, R' = OH, R''' = (CH2)2] in 1:2 molar ratio at room temperature, a
microcrystalline, yellow, eight-coordinate compound, [ZrL2] is obtained. On the other
hand, a mixture of 1:1 MeOH-Me2CO solution of TKACACZ, LH2 [26; R = R'' = H, R' =
OH, R''' = (CH2)2, 1,2-C6H4] and L'H2 [131; R = R' = H, R'' = (CH2)2OH and 25 (R = H, R'
= OH, R'' = 2-OH, 2-COOH)] in equimolar ratio on refluxing produces yellow, sevencoordinate heterochelates, [ZrLL']. They are sparingly soluble in most common organic
solvents. They get decomposed above 250 oC. LH2 behaves as a dibasic tetradentate
ONNO donor ligand in [ZrL2] and [ZrLL']. The heterochelate exhibits s(CO)(acac),
94
as(CO)(acac), (ZrO) and (ZrN) frequencies at 1580, 1400, 450 and 430 cm-1
respectively.
Macarovici et al.[140] have reported that a MeOH solution of HDAOHTZC and
LH2, 162 [R = R' = Me, R'' = (CH2)2, X = O] in 1:1 molar ratio produces a six-coordinate
compound, [ZrCl2 L]. However, a dark-brown resinous product, [ZrL2] is obtained[140] by
grinding an equimolar mixture of 162 [R = R' = Me, R'' = (CH2)2, X = O] and TKACACZ
and heating the mixture in vacuuo at 250 oC.
A DMF swollen suspension of PSCH2LH2 [53; R = R' = Me, R'' = (CH2)2; R =
NHPh, R' = Ph, R'' = (CH2)2] and a DMF solution of HDAOHTZAc on refluxing for 8 h,
produce[25,208] a cream coloured, seven-coordinate, polystyrene-anchored compound,
[PSCH2LZr(OH)2(DMF)]. Their PRCs are 54.8, 56.9 and the MBCs of the ligands are
0.36, 0.39 mmol of Zr per g of the ligands respectively. The IR data indicate the dibasic
tetradentate ONNO nature of the ligand. The compounds exhibit the (ZrOH) bending
mode at ~1130 cm-1. A pentagonal-bipyramidal structure has been assigned to them.
By mixing a MeOH solution of TKACACZ to a MeOH solution of LH2 [26; R =
R'' = H, R' = OH, R''' = (CH2)3] in 1:2 molar ratio, a light-yellow, eight-coordinate
compound, [ZrL2] is obtained[179]. The latter is sparingly soluble in most common organic
solvents and decomposes above 250 oC. LH2 behaves as a dibasic tetradentate ONNO
donor ligand. The compound exhibits (ZrO) and (ZrN) stretches at 450 and 430 cm1
respectively.
Islam et al.[209] have reported the synthesis of a six-coordinate compound,
[Zr(NCS)2L] [where LH2 = 26; R = R'' = H, R' = OH, R''' = (CH2)3]. The Schiff base
behaves as a dibasic tetradentate ONNO donor ligand.
The credit to synthesize for the first time an unsymmetrical polystyrene-anchored
mixed Schiff base, N,N'-propylenemono(3-carboxysalicylideneimine)mono(salicylideneimine), PSCH2LH2 and its coordination compound, [PSCH2LZr(OH)2(DMF)] goes to
Kumar and his team[210]. The PRC of the compound is 92.9 and the MBC of the ligand is
0.69 mmol of Zr per g of it. The (ZrOH) bending mode occurs at 1150 cm-1. A
pentagonal-bipyramidal structure has been suggested to the compound.
A yellow crystalline coordination compound, [ZrCl2L(THF)]THF (where LH2 =
26; R = R'' = H, R' = OH, R''' = 1,2-C6H4) is obtained by refluxing a THF solution of
95
[ZrCl4(THF)2] and disodium salt of LH2 in 1:1 molar ratio under inert atmosphere[203]. It is
fairly soluble in organic solvents and is very sensitive to moisture forming oxo compound.
LH2 acts as a dibasic tetradentate ONNO donor ligand.
On refluxing a MeOH solution of TKACACZ and LH2 (26; R = R'' = H, R' = OH,
R''' = 1,2-C6H4) in 1:2 molar ratio, a yellow, eight-coordinate compound, [ZrL2] is
obtained[179]. The latter decomposes above 250 oC. LH2 behaves as a dibasic tetradentate
ONNO donor ligand. The (ZrO) and (ZrN) stretches occur at 450 and 430 cm-1
respectively. The compound exhibits the peaks at m/e 718, 701, 612, 522 and 359 due to
the molecular ion [M]+, [MOH]+, [MC6H4CH2O]+, [MC6H5NCHC6H4O)]+ and
doubly charged parent chelate respectively[211].
The monomeric, eight-coordinate compound, [ZrL2] (where LH2 = 26; R = 3-F, R'
= OH, R'' = H, R''' = 1,2-C6H4) is obtained[212] by refluxing an EtOH solution of
[Zr(OBut)4] and LH2 in 1:2 molar ratio. LH2 coordinates as a dibasic tetradentate ONNO
donor ligand.
Illingsworth et al.[213] have become the first to synthesize an eight-coordinate
compound containing the uncoordinated ester groups. A bright-yellow coordination
compound, [ZrL2]EtOH [where LH2 = 26; R = R'' = H, R' = OH, R''' = 1,2-C6H3(5COOEt)] is obtained by refluxing
an EtOH solution of the Schiff base and [Zr(1-
OC4H9)(1-C4H9OH)] in N2 atmosphere. Owing to the presence of uncoordinated ester

group, it is fairly soluble in C6H6 and CH2Cl2. The IR data indicate the dibasic tetradentate
ONNO donor nature of LH2. The parent peak at 862 m/e corresponds to the [90ZrL2]EtOH
molecular ion peak. The [M17]+ and [M-280]+ peaks indicate the lose of one OH group
and OC6H4CH==NC6H3(N)COOC2H5 ligand fragment respectively from the compound.
The peak at m/e 149 is due to the MeOC6H3CH==N fragment.
The synthesis of a bright yellow, eight-coordinate compound, [ZrL2] (here LH2 =
26; R = R'' = H, R' = OH, R''' = 1,2-C6H4) has been reported[214]. The compound melts with
decomposition at 400 oC under N2. The Schiff base behaves as a dibasic tetradentate
ONNO donor ligand. The lattice parameters are: a = 13.037, b = 13.669, c = 14.500,
= 98.81o, = 116.47o and = 92.78o.
properties[215].
The compound has slight semiconducting
96
Tarafder et al.[216] have reported the synthesis of a six-coordinate peroxo
compound, [ZrO2L] (here LH2 = Schiff base derived from the condensation of
salicylaldehyde and hydrazine hydrate or 26 (R = R'' = H, R' = OH, R''' = 1,2-C6H4). The
Schiff base behaves as a dibasic tetradentate ONNO donor ligand.
Archer et al.[217] have claimed to become the first to synthesize a soluble, redglassy, non-volatile, linear polymer, [ZrL(DMSO)1.7]n (where LH4 = 163). The IR data are
indicative of the dibasic tetradentate ONNO donor nature of LH4. The polymer shows the
(S==O) stretch of coordinated DMSO at 1025 cm-1. The DTA of the polymer shows a
small endotherm between 130-190 oC due to the loss of water and DMSO. The polymer
starts burning in air at 380 oC.
Shafir et al.[218] have found that the monomerc, six-coordinate compounds,
[ZrL(CH2C6H5)2]S [where S = toluene, LH2 = 164 (R = CMe3, R' = H, R = R' = CMe3) or
165(R = R' = Me)] are obtained by stirring a toluene solution of LH2 and [Zr(CH2Ph)4] in
1:1 molar ratio. It is crystalline red when LH2 = 164 (R = CMe3, R' = H; R = R' = CMe3)
and crystalline yellow when LH2 = 165 (R = R' = Me).
The syntheses of the dimetallic, six-coordinate compounds, [ZrCl2L]2 (166 and
167, R = H, 3-MeO, 3-Me, 4-Me, 5-Me, 5-Cl) have been reported[219]. The IR data are
indicative of the dibasic tetradentate ONNO donor behaviour of the ligands. The
appearance of two bands between 450-550 cm-1 is due to the (ZrN) stretch and
suggests that the ligands occupy the cis-positions and the Cl atoms occupy the transposition. The compounds exhibit the (ZrO) stretch at ~ 450 cm-1
Ghose et al.[207] have synthesized five-coordinate compounds, [ZrOL] (where LH2
= 26; R = H, R' = OH, R'' = H, Me, R''' = 1,4-C6H4). The IR data indicate the dibasic
tetradentate ONNO donor behaviour of LH2.
An eight-coordinate polymer has been synthesized[220] by the reaction of LH2 (26;
R = R'' = H, R' = OH, R''' = 1,4-C6H4) and TKPZP. The polymer has low solubility in
common organic solvents. It is heat-resistant up to 400 oC and its average molecular
weight is 10650.
The synthesis of a six-coordinate compound, [ZrCI2L] (where LH2 = 26; R = R'' =
H, R' = OH, R''' = 4,4'-diphenyl) has been reported[221]. LH2 behaves as a dibasic
tetradentate ONNO donor ligand.
97
Woodman et al.[222,223] have claimed to be the first to synthesize a Zr(IV)
coordination compound containing a cis-cis-arrangement of a tetradentate ligand.
[ZrCl4(THF)2] reacts with LH2 (168) to form [ZrCl2L]. The X-rays studies of the latter
indicate that it has monoclinic unit cell. The two Cl ligands occupy mutually ciscoordination sites in a chiral ligand environment. The molecular structure of the
compound shows that it belongs to the cis-cis- class of tetradentate Schiff base
coordination compounds.
Dey et al.[224] have synthesized a yellow-brown, amorphous, seven-coordinate
compound, [Zr(OH)2L(THF)] and another monomeric, brown, six-coordinate compound,
[Cp2ZrL] [here LH2 = 120; R = R' = Me, R'' = R''' = NHCOC6H4(4-OMe)]. They are
soluble in DMSO, DMF, MeOH, EtOH, Me2CO etc. The IR data indicate a dibasic
tetradentate ONNO donor nature of LH2.
Tarafder et al.[225] have synthesized a six-coordinate, non-electrolyte (in DMSO),
peroxo compound, [ZrO2L] [where LH2 = 120; R = R' = Ph, R'' = R''' = NC(SH)SCH2Ph].
LH2 behaves as a dibasic tetradentate SNNS donor ligand. The compound shows the
(C==N), (CS), 1(OO), 3(ZrOO), 2(ZrOO), (ZrN) and (ZrS) stretches
at 1520, 710, 820, 650, 550, 325 and 270 cm-1 respectively.
On refluxing an EtOH solution of Zr(NO3)45H2O and an EtOH solution of LH2
(169) for 5 h, a cabinet-grey, seven-coordinate compound, [ZrO(NO3)2(LH2)]2H2O is
obtained[226]. An EtOH suspension of this compound on treating with ClCH2COOH in 1:1
molar ratio followed by refluxion for 4 h, produces another cabinet-grey, seven-coordinate
compound, [ZrO(NO3)2(L'H2)]2H2O (where L'H2 = 170). The compounds are nonhygroscopic, highly stable under normal conditions and decompose above 250 oC. They
are insoluble in H2O, MeOH, EtOH, Me2CO, CHCl3, CCl4, C6H6 and EtOEt but are
moderately soluble in DMF and DMSO. They are non-electrolytes, however, due to their
partial solvolysis in DMSO, their experimental conductance values (M = 38.52 and 33.82
mho cm2 mol-1) are higher than the expected values for non-electrolytes. The compounds
remain almost unaffected up to ~70 oC. Both the water molecules are lost by heating them
at 110 oC. The anhydrous compounds remain stable up to ~370 oC. ZrO2 is the final
product at 750 oC. They exhibit (ZrN) vibrations at ~480 cm-1. The appearance of new
98
additional bands at ~1385 and 1050 cm-1 corresponding to the 2 and 4 vibration modes
indicates the presence of monodentate nitrato groups in the compounds.
E.
With polydentate ligands:

Relatively little work has been reported on Zr(IV) coordination compounds with a
Schiff base containing five- or six-donor sites. Schweder et al.[204] have synthesized
[ZrCl2L] [where LH2 = N,N-bis(ethylene)-N-methyl-N,N-bis(benzoylacetonatoimine)].
LH2 behaves as a dibasic pentadentate ligand and lies in the plane. Both chloro groups
occupy the axial positions and Zr attains a pentagonal-bipyramidal environment. In
contrast to the catalytically active salen coordination compounds, this compound does not
rearrange to form a species in which both the chloro groups are cis-to each other.
Consequently, it is catalytically inactive.
Islam et al.[209] have reported the synthesis of isothiocyanato compound,
[Zr(NCS)2(LH2)] (where LH4 = 78; R = H). LH4 acts as a dibasic hexadentate O2N4 ligand.
The isothiocyanato ligands are connected to Zr through their N atom(s).
Dimeric,
six-coordinate
compounds,
[(ZrO)2(NO3)2L(H2O)2]
have
been
synthesized by template method by refluxing an EtOH solution of Zr(NO3)44H2O,

thiocarbohydrazide, diacetyl/benzylmonohydrazone and salicylaldehyde[227]. They remain
almost unaffected upto 130 oC and decompose above 250 oC. The coordinated H2O
molecules are lost between 130-190 oC. The anhydrous compounds remain stable up to
375 oC. Finally, ZrO2 is obtained at 675 oC. Though the compounds are non-electrolytes
but exhibit somewhat higher values (M = 22.66-24.18 mho cm2 mol-1) due to their partial
solvolysis in DMSO. They exhibit (ZrO) and (ZrN) vibrations at 520-540 and
~475 cm-1 respectively. Nitrato groups are bonded to Zr in a monodentate fashion.
Coordination compounds of molybdenum(VI)

Molybdenum (Mo) is a silvery-greyish 4d- transition metal and belongs to Group
6, Period V of the Periodic Table. Its atomic number, atomic weight and the electronic
configurations are 42, 95.94 amu and [Kr] 4d55s1 respectively. Although molybdenum
exhibits a variety of oxidation states (2, 0, +1, +2, +3, +4, +5 and +6), the +6 state is the
most stable and thoroughly investigated state, where it forms a large number of
coordination compounds. The latter containing the oxomolybdenum group dominate the
99
higher oxidation states. The Chemistry of hexavalent molybdenum is dominated by the
oxo ligand and its analogues. The compounds containing cis-MoO22+ unit are
characterized by two infrared active frequencies; s(O==Mo==O) and as(O==Mo==O)
stretches lying between 862-964 cm-1 and 842-928 cm-1 respectively, reported for the
majority of MoO22+ compounds. A compound with trans-MoO22+ structure has been
reported to exhibit only the as(O==Mo==O) stretch since the s(O==Mo==O) stretch is IR
inactive[228,229]. Molybdenum is an essential trace element for animals and plants. Owing
to the importance in numerous biochemical redox reactions associated with enzymes, a
considerable interest in the coordination compounds of molybdenum has drawn the
attention of Chemists in the past. It is the only element among the heavier transition
elements which appears to have a major role as a trace element in enzymes. It is also one
of the most biologically active elements and is an essential micronutrient for
microorganisms, animals and plants[230]. Nature has incorporated molybdenum into a
number of redox enzymes. About 20 different enzymes containing molybdenum are
known in animals, including nitrogenase, aldehyde oxidase, sulphite oxidase and xanthine
oxidase. In these enzymes, molybdenum cycles between +4 and +6 oxidation states in
their reactions with substrate and subsequent reactivation. Enzymes such as nitrogenase,
nitrate reductase, xanthine dehydrogenase, xanthine oxidase, sulphite oxidase and
aldehyde oxidase contain molybdenum atoms bonded through O, N and/or S atoms. These
Mo sites are supposed to be active centers for the catalytic activity of the enzymes[231]. In
nitrogenase enzyme, it is actively involved in N2 fixation. Mo concentration also affects
protein synthesis, metabolism and growth. It is transported throughout the human body as
MoO42. The O atom transfer properties of the MoO2(VI) compounds play a significant
role in investigating the mechanism of Mo oxotransferase[232]. The ability of MoO2(VI) ion
to form the coordination compounds with a wide range of ligands has been reported. These
ligands are coordinated to MoO2(VI) ion in a monodentate, bidentate, tridentate and
tetradentate fashion. We present here a brief survey of the Chemistry of coordination
compounds of MoO2(VI) ion.
A.

Cindric et al.[233] have claimed to become the first to synthesize the monomeric, air
and
moisture
stable,
yellow
crystalline,
six-coordinate
compound,
100
[MoO2(LH)(OMe)(acac)] (where LH = 131; R = H, 5,6-benzo, R' = H, R'' = C6H5,
CH2C6H5). They are obtained by refluxing a MeOH solution of [MoO2(acac)2] and LH in
1:1 molar ratio for 1 h. Interestingly, instead of the deprotonation of the Schiff base, the
reaction takes place by the deprotonation of MeOH. It is worth to mention that potentially
the bidentate ON donor ligand is bonded to the metal ion through its phenolic OH group
and not through the azomethine N atom. The s(O==Mo==O) and the as(O==Mo==O)
stretches occur at ~930 and 900 cm-1 favouring the presence of cis-MoO2 structure. The
compound (when R = H) crystallizes in a triclinic fashion with a = 8.0478 , b = 10.2829
, c = 13.7790 , = 76.541o, = 82.295o and = 77.4o. Within the same ligand, the
phenolic H atom is attached to azomethine N atom and forms an intramolecular H-bond of
2.548 with the O atom coordinated to Mo. The octahedral coordination of Mo is
completed by two oxo-O, two acetylacetonato O and one O atom each of LH and methoxo
ligand. A distorted octahedral structure [171; R = H, 5,6-benzo, R' = C6H5 or CH2C6H5]
has been suggested to it.
B.

The syntheses o f yellow to red six-coordinate compounds, [MoO2L2] (where LH
= monobasic bidentate Schiff base, 131; R = H, 3-Me, 3-MeO, R' = H, R'' = Me, Et, 1-Pr,
1-Bu, 1-C7H15, C6H5, 4-EtC6H4, 4-FC6H4, 3-ClC6H4, 4-ClC6H4, 4-BrC6 H4, 4-IC6H4, 4OHC6H4, 4-NO2 C6H4 and CH2 C6H5, 3-MeC6H4, 4-MeC6H4, 2-OMeC6H4, 4-OMeC6H4,
3,4-Cl2 C6H3) have been reported[234-236]. They are sparingly soluble in MeOH, EtOH,
CH2Cl2 and CHCl3. The single crystal X-rays structure of [MoO 2 L 2 ] (when R = H, R' =
H, R'' = 1-Pr) has cofirmed the presence of a cis-MoO2 octahedral environment in it[237].
Zelentsov et al.[238] have synthesized the compounds, [MoO2L2] (where LH = 25;
R = R'' = H, R' = OH). LH behaves as a monobasic bidentate ON donor ligand. The
syntheses of [MoO2L2] (where LH = 25, R = H; R' = OH; R'' = H, 5-Cl, 5-Br, 5-NO2, 5OMe have been reported[239-245]. The IR data are indicative of the monobasic bidentate
ON donor nature of LH.
The syntheses of [MoO2(LH)2] and [MoO2(L'H2)2] (where LH2 = 131; R = H, R' =
Me, R'' = OH and L'H3 = 131; R = 4-OH, R' = C4H9, R'' = OH) have been reported[246].
LH2 and L'H3 behave as monobasic bidentate ON donor ligands.
101
Although LH2 (25; R = H, R' = OH, R'' = 2-SH), L'H2 (25; R = H, R' = OH, R'' =
2-OH) and L''H2 (25; R = H, R' = OH, R'' = 4-COOH) are potentially the dibasic tridentate
ONS/ONO donor ligands, but behave[2 4 7 ] as the monobasic bidentate ON donor ligands in
[MoO2(LH)2], [MoO2(L'H)2] and [MoO2(L''H)2] respectively. During the course of
reaction, LH2 (25; R = H, R' = OH, R'' = 2-SH) undergoes cyclization and is converted to
172, which is coordinated to the metal ion in ON donor fashion.
The synthesis of six-coordinate heterochelate, [MoO2(acac)(LH)] (here LH 2 =
25; R = H, R' = OH, R'' = 2-COOH) has been repo rt ed [248]. The monobasic ligand
coordinates to the metal ion through its carboxylic O and azomethine N atoms.
Poddar et al.[249] have synthesized the monomeric, six-coordinate compound,
[MoO2Cl2(LH2)] (where LH2 = 52; R = (2-OH)C6H4CH, R' = C6H5, C6H4(2-NH2),
C6H4(4-NH2), X = O).
A yellow, six-coordinate compound, [PSCH2LMoO2(acac)] (here PSCH2LH =
68) has been synthesized[2 5 0 ] by reacting [MoO2(acac)2] and PSCH2 LH in DMF. It
exhibits the s (O==M==O) and the a s (O==M==O) stretches at 935 and 905 cm-1
respectively. The PRC of the compound and the MBC of the ligand are 91.4 and 1.31
mmol of metal per g of the latter respectively.
C.

The syntheses of the compounds of LH2, [131; R = H, 5-Cl, 5-Br, 5-NO2, 5-Me,
5-OMe, 5,6-C4H4, R' = H, R'' = (CH2)2OH] have been reported by a number of

researchers[242,243,251]. The compounds are of types, [MoO2L] or [MoO2 LS] (here S = H2O,
EtOH). On heating at 100
C, the monomeric, yellow coordination compound,
[MoO2L(H2 O)] and [MoO2L(EtOH)] form the brown, five-coordinate, oligomeric

compound, [MoO2L] (173, X = O). The latter upon solvation with DMF or DMSO forms
the six-coordinate solvated adduct, [MoO2LA] (174, X = O, A = DMF, DMSO) which
exhibits two bands between 890-925 and 910-950 cm-1 due to the as(O==Mo==O) and
the s(O==Mo==O) stretches respectively. However, [MoO2L] exhibits only one band at
930 cm-1 due to the (Mo==O) stretch and a strong band at ~800 cm-1 due to the
Mo ==OMo ==O stretch suggesting oligomeric structure (173, X = O).
Kumar et al.[10] have synthesized a light-yellow, polystyrene-anchored sixcoordinate compound, [PSCH2LHMoO2(DMF)] (where PSCH2LH3 = 34) by refluxing a
102
DMF swollen suspension of PSCH2LH3 and a DMF solution of [MoO2(acac)2] . The
PRC of the compound is 76.4 and the MBC of PSCH2LH3 is 0.50 mmol of Mo per g of
the ligand. PSCH2LH3 behaves as a dibasic tridentate ONO donor ligand. The compound
exhibits two strong absorbtion bands at 950 and 915 cm-1 due to the s(O==M==O) and
as(O==M==O) stretches respectively.
The syntheses of the oligomeric coordination compounds, [MoO2(LH)] [where
LH3 = 113 (R = CH2C6H4(2-OH), C10H6COOH)], [MoO2(L'H)], [here L'H3 = 113, R =
C6H4(2-OH)], [MoO2L''] [here L''H2 = 131; R = H, 5,6-benzo, R' = H, R'' = CH2C6H4(2OH)], their monomeric, six-coordinate adducts, [MoO2(LH)A], [MoO2(L'H)A],
[MoO2L''A] (here A = H2O, MeOH, py, DMSO) and monomeric, seven-coordinate
heterochelates, [MoO2(LH)B] and [MoO2 L''B] (B = bipy) have been reported[252,253]. The
compounds and adducts/heterochelates are insoluble in H2O but soluble in MeOH, EtOH,
py, DMF, DMSO and are non-electrolytes in DMF. They exhibit a band at ~930 cm-1 due
to
the (Mo==O)
stretch and
a strong
band
at
~770
cm-1 due to
the
Mo ==OMo ==O interaction suggesting their oligomeric structure (173, X = O).

The absence of a band at ~770 cm-1 in [MoO2(LH)A], [MoO2(L'H)A], [MoO2L''A]
indicates the breaking of oligomeric chains and the formation of monomeric adducts. This
also indicates that oligomerization takes place via O bridge involving O atom of MoO2
moiety. The Schiff bases behave as the dibasic tridentate ONO donor ligands in the
compounds
and
adducts/heterochelates
coordinating
through
their
phenolic
and/carboxylic O and azomethine N atoms, while B acts as a neutral bidentate NN donor

ligand in the heterochelates. The alcoholic O atom of pyridoxal moiety does not take part
in the coordination. An octahedral structure (174, X = O, A = H2O, MeOH, py, DMSO)
for the adducts and a pentagonal-bipyramidal structure (174, X = O, A = bipy) have been
suggested for the heterochelates.
The synthesis of the oligomeric coordination compounds, [MoO2L] [where LH2 =
131; R = H, 5,6-benzo, R' = H, R'' = CH2C6H4(2-OH); R = 5,6-benzo, R' = H, R'' =
C6H4(2-CH2OH)] and [MoO2L'(MeOH)]2MeOH [here L'H2 = 131; R = H, R' = H, R'' =
C6H4(2-CH2OH)] have been reported[254]. [MoO2L] [R = H, R' = H, R'' = CH2C6H4(2OH)] is greenish-yellow and decomposes at 300 oC, while [MoO2L] [R = 5,6-benzo, R' =
H, R'' = CH2C6H4(2-OH)] is brown and decomposes at 325 oC. They are soluble in py,
103
DMF, DMSO. They are non-electrolytes in DMF (M = 3-7 mho cm2 mol-1).
[MoO2L'(MeOH)]2MeOH loses the coordinated and non-coordinated MeOH molecules at
170 oC and forms, [MoO2L']. The latter starts decomposing at 280 oC and continues upto
580 oC. [MoO2L] exhibits only one (O==M==O) stretch between 918-955 cm-1 and a
sharp broad band between 695-770 cm-1 due to the (M==O) stretch as a result of
Mo ==OMo ==O interaction suggesting their oligomeric structure (173, X = O).
The as(O==M==O) and the s(O==M==O) stretches occur at 911 and 933 cm-1 in
[MoO2L'(MeOH)]2MeOH respectively. LH2 and L'H2 behave as the dibasic tridentate
ligands coordinating through their phenolic O, azomethine N and alcoholic O atoms. A
distorted-octahedral geometry has been suggested for [MoO2L'(MeOH)]2MeOH.
The reaction of [MoO2(acac)2] with LH2 (96; R = R'' = H, R' = OH, R''' = CHMe2
or 128) in H2O/MeOH solution (1:1 v/v) forms[254] the six-coordinate, oligomeric
compound, [MoO2L]. Casella et al.[255] have synthesized a six-coordinate, monomeric
compound, [MoO2 L(H2O)] (here LH2 = Schiff base obtained from the condensation of
pyrrol-2-aldehyde and valine). The Schiff base, LH (a condensation product of pyridine2-aldehyde and valine) forms[255] a monomeric heterochelate, [MoO2L(acac)].
Dutta et al.[245] have synthesized the monomeric, six-coordinate compounds,
[MoO2(LH)(H2 O)] and [MoO2(LH)(EtOH)]
[here LH3 = 52; R = (2-OH)C6H4CH,
(2-OH)C10H6CH, R' = C6H4(2-OH)]. The former is obtained by refluxing a MeOH

solution of [MoO2(acac)2] and LH2 in 1:1 molar ratio, while the latter is obtained by
refluxing an EtOH solution of Na2 MoO4 and LH2 in 1:1 molar ratio.
An orange, non-electrolyte, [MoO2(LH)(H2O)] [LH3 = 52; R = (2-OH)C6H4CH, R'
= C6H4(2-OH)] is obtained[256] by the reaction of [MoO2(acac)2] and LH3 in 1:1 molar
ratio. It is soluble in DMF, DMSO, MeCN, MeOH and CH2Cl2. The compound on
crystallization from MeOH results in formation of [MoO2(LH)(MeOH)]. It shows O atom
transfer reaction to PPh3.
The
monomeric,
brown-red/orange-red,
six-coordinate
compounds,
[MoO2(LH)(H2O)] [where LH3 = 52; R = (2-OH)Y-C6H3CH, R' = C6H4(2-OH), Y = H, 5Cl, 5-Br, 5-NO2, 3-OMe, 3-OEt, 3,5-Cl2, 5,6-benzo], [MoO2(LH)(THF)] [here LH3 = 52;
R = (2-OH)C6H4CH, R' = C6H4(2-OH)], [MoO2(L'H)S] [here L'H3 (52; R = (2OH)C6H4CH, (2-OH)C10H6CH, (2-OH)C6H4CMe, (2-OH)C10H6CMe, R' = C6H3(2-
104
OH)Me, S = H2O, py) and [MoO2(L'H)(THF)] [LH3 = 52; R = (2-OH)C6H4CH, R' =
C6H3(2-OH)Me] have been synthesized[257,258]. The compounds/adducts are insoluble in
H2O but soluble in MeOH, EtOH, DMF, DMSO, THF and dioxane. They are nonelectrolyte in THF ( M = 0.19-8.7 mho cm2 mol-1). [MoO2(L'H)S] (S = H2O, py, THF)
shows the weight loss between 95-150 oC due to the loss of H2 O, THF or py molecules.
[MoO2(L'H)(H2O)] [LH2 = 52; R = (2-OH)C6H4CH, R' = C6H3(2-OH)Me] loses H2O
molecule between 95-100
C. The mass loss occurs at 200-480
C due to the
decomposition of organic skelton resulting in formation of MoO3 between 460-480 oC.

On subsequent heating continuous mass loss is attributed to the volatile nature of MoO3.
LH3 behaves as a dibasic tridentate ONO donor ligand in the compounds/adducts
coordinating through its phenolic O, azomethine N and enolic O atoms. The compounds
exhibit the s(O==M==O) and as(O==M==O) stretches between 915-950 and 890-925
cm-1 respectively. The former band gets splitted in some compounds by ~10 cm-1 due to
the crystal packing effect. The replacement of H2O by THF or py in [MoO2(L'H)S] (S =
H2O, py, THF) affects the energy difference () between s(O==M==O) and
as(O==M==O) stretches. is in the order H2O >THF > py. A monomeric structure (174;
X = O, A = H2O, py, THF) with planar tridentate ligands occupying meridional position
is suggested for them.
Prabhakaran et al.[259] have observed that the energy separation () between
s(O==M==O) and as(O==M==O) stretches in [MoO2(LH)S] (where LH3 = 52; R =
(2-OH)C6H4CMe, R' = C6H4(2-OH), S = H2O, DMF, DMSO, THF or py-N-oxide) is in
the order: H2O > DMF > py-N-oxide > THF > DMSO and the thermal stability of the
compounds is in the order: H2O > py-N-oxide > DMSO > DMF > THF.
Gupta et al.[260] have synthesized the orange-yellow compound, [MoO2L(EtOH)]
(where LH2 = 175; R = H, Me, R' = H, Br, NO2) by refluxing an EtOH solution of
[MoO2(acac)2] and LH2 in 1:1 molar ratio. The compound (when R = H, R' = NO2) is the
most easily reducible by electrochemical studies. It undergoes oxo abstraction reaction at
room temperature even at small concentration (~10-4 mol/L) resulting in the reduction of
Mo(VI) to Mo(IV) compound during the course of oxo transfer reaction towards PPh3.
The monomeric, non-electrolyte (M = 1.5-9.1 mho cm2 mol-1 in DMF), sixcoordinate compounds, [MoO2 L(MeOH)] (here LH2 = 176; R = H, 5,6 benzo) are
105
obtained by refluxing a MeOH solution of [MoO2(acac)2] and LH2 in 1:1 molar ratio for 2
h[261]. They are sparingly soluble in MeOH and EtOH. The coordinated MeOH molecule
is lost at ~110 oC. The s(O==M==O) and as(O==M==O) stretches occur at 935-940 and
910 cm-1 respectively. The S atom of benzothiazole moiety does not take part in
coordination.
The monomeric, yellowish-brown, six-coordinate compound, [PSLMoO2(DMF)]
(where PSLH2 = 177) is obtained by refluxing a DMF solution of [MoO2(acac)2] and
PSLH2 in 1:1 molar ratio for 7 h[262]. The PRC of the compound is 70.9. The MBC of the
ligand is 0.89 mmol of metal per g of it. The Schiff base acts as a dibasic tridentate ONO
donor ligand. The compound exhibits the s(O==M==O) and as(O==M==O) stretches at
950 and 910 cm-1 respectively.
The synthesis of a six-coordinate compound, [MoO2Cl(LH2)] (here LH3 = 178)
has been reported by Devi et al. [263]. It is stable and soluble in MeOH and CHCl3. LH3
acts as a monobasic tridentate ONO donor ligand.
The syntheses of the coordination compounds with dibasic tridentate ONS donor
ligands [131; R = H, 5-Cl, 5-Br, 5-NO2, 5-Me, 3-C4H9, 5-C4H9, 5-OMe, 5,6-C4H4, R' = H,
R'' = (CH2)2SH] have been reported[239-244,251]. Their stoichiometries are, [MoO2L] and
[MoO2LA] (A = H2 O, EtOH).
The synthesis of a dimeric, six-coordinate compound, [MoO2 L]2 (where LH2 = 25;
R = H, R' = OH, R'' = 2-SH) has been reported[251]. An octahedral structure (179)
involving phenoxo bridges has been suggested.
Although LH4 (180; R = H, Br, NO2, Y = H, Me) is potentially a dibasic
pentadentate ONSNO donor ligand, but behaves[264] as a dibasic tridentate ONS donor
ligand in orange-red, six-coordinate, non-electrolyte (in DMF), [MoO2(LH2)(MeOH)].
The (MoO) and (MoN) stretches appear at ~595 and between 510-560 cm-1
respectively.
A dimeric, six-coordinate compound, [(MoO2py)2L] (where LH4 = 181; R = H,
OMe, n = 0, 1, 2, 4, 8) has been synthesized[265]. The py molecules are lost between 150200 oC. An octahedral structure (182; R = H, OMe) has been suggested to it.
106
D.

The reaction between MoCl6 and LH2, 183 [here R = (CH2)n; n = 2-6] forms the six-
coordinate compound, [MoO2L][266]. The ligand is coordinated through two azomethine N

and two deprotonated O atoms of oxime moieties.
Dey et al. [242] have synthesized the monomeric, six-coordinate compound, [MoO2L]
[where LH2 = 162; R = R' = Me, R'' = (CH2)2, 1,2-C6H4, X = O]. The Schiff bases act as
the dibasic tetradentate ONNO donor ligands.
Yamanouchi et al. [234] have synthesized the six-coordinate compound, [MoO2L]
[here LH2 = 26; R = H, 3-OMe, R' = OH, R'' = H, Me, R''' = (CH2)2, (CH2)3, (CH2)4,
(CH2)6, CH(Me)CH2, (CH2)2NH(CH2)2, 1,2-C6H4].
Kudryavstev et al. [267] have synthesized the monomeric, six-coordinate compound,
[MoO2L] [here LH2 = 26; R = H, 4-Me, 5-Br, R' = OH, R'' = H, R''' = (CH2)2] by the
reaction of an ether solution of MoO2Cl2 and the Schiff base in 1:1 molar ratio. LH2 acts
as a dibasic tetradentate ONNO donor ligand.
Kumar et al. [25] have synthesized a yellowish-brown, monomeric, six-coordinate
polystyrene-anchored coordination compound, [PSCH2LMoO2] [where PSCH2LH2 =
53; R = R' = Me, R'' = (CH2)2]. It is insoluble in water as well as in other organic solvents.
PSCH2LH2 acts as a dibasic tetradentate ONNO donor ligand coordinating through its
phenolic O, azomethine N and enolic O atoms. The compound exhibits the s(O==M==O)
and as(O==M==O) stretches at 940 and 900 cm-1 respectively indicating the presence of
a cis-MoO2 structure. The PRC of the compound is 39.4 and MBC of the ligand is 0.27
mmol of metal per g of resin.
Syamal et al. [268] have synthesized a yellow, six- coord inat e compound, [PSCH2
LMoO2] (where PSCH2LH2 = 184) by refluxing [MoO2(acac)2] and PSCH2LH2 in 1:1
molar ratio in ethyl acetate and DMF for 8 h. The Schiff base acts as a dibasic tetradentate
ONNO donor ligand. The s(O==M==O) and as(O==M==O) stretches occur at 960 and
895 cm-1 respectively. The cis-MoO2 structure of the compound forces the ligand to
coordinate in a non-planar fashion. The PRC of the compound and MBC of the ligand are
66.5 and 1.01 mmol of metal per g of the resin respectively.
Ambroziak et al.[269] have reported the syntheses of [MoO2L] [where LH2 = 185; R
= H, 3,5-Cl2, 3,5-Br2, 5-NO2, 4,6-(OMe)2]. The compounds are slightly soluble in organic
107
solvents, while fairly soluble in HCCl2CCl2H and DMSO. They exhibit two bands at 928
and 872 cm-1 due to the s(O==M==O) and the as(O==M==O) stretches. The presence of
electron donor substituents in the salicylidene ring strengthen the MoN bond and
increases the stability of the compound, while the electron withdrawing groups decrease
their stability.
The binuclear, ligand-bridged, six-coordinate, non-electrolyte heterochelates,
[MoO2(acac)LMoO2(acac)] [here LH2 = 183; R = (CH2)2, (CH2)3, (CH2)2NH(CH2)2,
(CH2)2NH(CH2)2NH(CH2)2] are obtained[270] by the reaction of [MoO2(acac)2] and
LH2. Each MoO2(VI) ion is surrounded by one bidentate acac group and two N-donor
atoms (oxime N and imine N) of the ligand. The latter behaves as a dibasic tetradentate
N4 donor ligand bridging two MoO2(acac)+ centres. The presence of two intense bands
between 880-920 cm-1 due to the s(O==M==O) and as(O==M==O) stretch indicates the
presence of a cis- MoO22+ group in the heterochelates. An octahedral structure (186, R =
as above) has been suggested for the heterochelate.
Kudryavstev et al. [267]
have synthesized the monomeric, eight-coordinate
compound, [MoO2Cl2 L)] [here L = 26; R = R'' = H, R' = NH2, R''' = (CH2)2, 1,2-C6H4] by
the reaction of an ether solution of MoO2 Cl2 and the Schiff base in 1:1 molar ratio. L acts
as the neutral tetradentate N4 donor ligand.
E.
With polydentate ligands:

The syntheses of binuclear coordination compound, [(MoO2)2L] (where LH4 =
flexibly-bridged tetrabasic hexadentate Schiff base obtained from the condensation of

methylene- or dithiobis(salicylaldehyde) with 2-aminoethanol, 2-amino-2-methylpropanol,
1-amino-2-propanol,
2-aminophenol,
S-methyldithiocarbazate
and
S-
benzyldithiocarbazate) have been reported[271,272]. Each MoO2(VI) ion achieves a pseudooctahedral oligomeric structure via Mo==OMo bridging. [(MoO2)2L] reacts with py and
forms the corresponding adduct, [MoO2)2L(py)2]. Here py binds at the sixth labile sites in
both [MoO2]2+ units. The oligomeric coordination compounds show the (Mo==O)
stretches between 910-938 cm-1 and the (Mo==O) band at ~820 cm1 due to Mo==O
Mo interaction. In a single endothermic step at 180C, [(MoO2)2L(py)2] loses py and gets
converted to [(MoO2)2L].
108
Coordination compounds of cadmium(II)
Cadmium (Cd) is a soft bluish-white metal belonging to Group 12 and Period V of
the Periodic Table. Its atomic number, atomic weight and the electronic configurations are
48, 112.41 amu and [Kr] 5s24d10 respectively. Its most common oxidation state is +2. It is
highly toxic and carcinogenic metal. The ability of Cd(II) ion to form the coordination
to Cd(II) ion in a monodentate, bidentate, tridentate, tetradentate, pentadentate and
hexadentate fashions. We present here a brief survey of the Chemistry of the coordination
compounds of Cd(II) ion.
A.

Tian et al.[273] have synthesized a mononuclear, four-coordinate compound,
[CdBr2(LH)2] (where LH = 52; R = 2-ClC6H4CH, R' = NH2, X = S). The coordination

geometry about the Cd(II) ion in the compound conforms to a tetrahedral configuration
with two S atoms from two neutral monodentate ligands and two bromo groups. The
synthesis of a dinuclear, five-coordinate compound, [CdI2(LH)2]2 [where LH = neutral
monodentate ligand, 52; R = 2-ClC6H4CH, R' = NH2, X = S) has also been reported[273].
The latter crystallizes in a monoclinic fashion with a = 12.964 , b = 5.131 , c = 4.970
, = = 90.0o, = 94.32 and Z = 4. A distorted trigonal-bipyramidal iodo-bridged
structure (187; X = I, X' = Cl) has been proposed for it.
Duan et al.[274] have reported the synthesis of a dinuclear, five-coordinate
compound, [CdI2(LH)2]2 (where LH = 52; R = 2-BrC6H4CH, R' = NH2, X = S). LH acts as
a neutral monodentate ligand. The Cd(II) ion is ligated to thiosemicarbazone S atoms and
two iodo groups, out of which one I is present at the bridging position in the dinuclear
compound. A distorted trigonal-bipyramidal iodo-bridged structure (187; X = I, X' = Br)
has been proposed for it.
B.

The reaction of 2-aminophenol with Cd(II) ions in the presence of
4-benzyloxybenzaldehyde or but-2-enal in 1:1:1 molar ratios yields[4] the yellow

compound, [CdL2] or orange-yellow compound, [CdL'2] respectively (where LH and L'H
= 28 and 29 respectively). [CdL2] and [CdL'2] melt at 280 and 190 oC respectively. Both
LH and L'H act as monobasic bidentate ON donor ligands. [CdL2] displays the (CdO)
109
and (CdN) vibrations at 590 and 497 cm-1 respectively, while [CdL'2] displays these
vibrations at 570 and 449 cm-1 respectively. The compounds are more biologically active
against S. dysenteria, E. coli, P. aeruginosa, B. subtilis, S. lutea and S. aureus than 2aminophenol.
A white, six-coordinate, non-electrolyte (M = 10.1 mho cm2 mol-1 in DMSO),
[CdCl2(LH2)2] (here LH2 = 84; R = 4-OH, R' = Me) has been synthesized by refluxing an
H2O/EtOH solution of CdCl2H2O and LH2 in 1:1 molar ratio for 8 h[56]. It is insoluble in
Me2CO, CHCl3 and C6H6 but is fairly soluble in DMF and DMSO. It decomposes between
230-232 oC. LH2 acts as a neutral bidentate ON donor ligand. The latter shows higher
antibacterial activity against E. coli than LH2, whereas the antifungal activity of the former
against A. niger is less than it. An octahedral structure (85; M = Cd) has been suggested
for it.
An EtOH solution of formylferrocenyl-3-hydroxy-2-naphthoylhydrazone (LH2)
(30; R = H) and Cd(NO3)24H2O in 2:1 molar ratio upon refluxing in the presence of TEM
produces[6] a red compound, [Cd(LH)2]. The latter decomposes at 281 oC. Its molar
conductance is 23 mho cm2 mol-1. LH2 acts as a monobasic bidentate ON donor ligand.
The synthesis of a dinuclear, four-coordinate non-electrolyte, [Cd2L2] (here LH2 =
87; R = H, 5,6-benzo) has been reported[58]. The compound is white (when R = H) and red
(when R = 5,6-benzo). They are amorphous in nature, having high melting points and are
feebly soluble in DMF and dioxane. LH2 behaves as the monobasic bidentate ON donor
ligand coordinating through its phenolic O and azomethine N atoms. The (CdO) and
the (CdN) vibrations occur at ~500 and ~350 cm-1 respectively. A tetrahedral structure
has been suggested for the compound.
Kumar et al.[25] have synthesized a cream coloured, four-coordinate polystyreneanchored compound, [PSCH2LCd(OAc)(DMF)] (where PSCH2LH = 68) by refluxing a
DMF swollen suspension of PSCH2LH and Cd(OAc)22H2O in 2:1 molar ratio. The
Schiff base acts as a monobasic bidentate ON donor ligand.
A four-coordinate, tan coloured complex, [CdCl2(LH2)] is obtained[275] by
refluxing an EtOH solution of CdCl26H2O and LH2 in 1:1 molar ratio for 8 h. The
complex melts at >260 oC. The (C==O)(carbonyl) and (C==N)(azomethine) stretches of
the ligand occurring at 1625 and 1565 cm-1 shift to 1615 and 1550 cm-1 respectively in the
110
complex. LH2 acts as a neutral bidentate ligand coordinating through both azomethine N
atoms.
An orange, non-electolyte coordination compound, [CdL2] (where LH = 188) has
been synthesized by reacting an EtOH solution of CdCl2H2O and LH in the presence of
KOH[276]. The Schiff base acts as a monobasic bidentate NS donor ligand.
An aqueous solution of Cd(OAc)22H2O on treating with an hot EtOH solution of
LH (127; R = 4-NMe2, R' = H, R'' = Et) in 1:2 molar ratio forms[115] a white, sixcoordinate compound, [CdL2(H2O)2]. It is insoluble in common organic solvents and does
not melt even up to 300 oC. LH acts as a monobasic bidentate NS donor ligand.
Ramachandra et al.[129] have synthesized a four-coordinate, non-electrolyte,
[Cd(LH)2] (where LH2 = 139) by refluxing the metal ions and LH2 in 1:2 molar ratio in
EtOH. The IR data are indicative of the monobasic bidentate NS donor behaviour of the
ligand. The compound exhibits the (CdN) and (CdS) vibrations at 470 and 330 cm-1
respectively.
C.

The monomeric, cream coloured, four-coordinate polystyrene-anchored compound,
[PSLCd(DMF)] (where PSLH2 = 31) is obtained by refluxing a DMF swollen

suspension of PSLH2 and Cd(OAc)22H2O for 8 h[7]. The PRC of the coordination
compound is 75.3 and the MBC of the ligand is 0.61 mmol of metal per g of it. The IR
data are indicative of the dibasic tridentate ONO donor nature of the ligand.
A MeOH solution of Cd(NO3)24H2O reacts with LH2 (96; R = R''' = H, R' = OH,
R'' = Me) and L' [26; R = R' =R'' = H, R''' = (CH2)2] or L'' (110; R = 4-Me, X = S) and
forms the yellow, six-coordinate heterochelates, [CdLL'(H2O)] and [CdLL''(H2O)]
respectively[277]. The heterochelates are soluble in DMSO. The IR data are indicative of
the dibasic tridentate ONO donor behaviour of LH2 and neutral bidentate NN or NS donor
behaviour of L' or L'' respectively. Between 50-800 C, the heterochelates decompose in
two steps. In the first step, a loss of the coordinated H2O molecule takes place, whereas at
high temperature, the ligand molecules are lost resulting in the formation of metal oxide as
the end product. The heterochelates are better antifungal agents towards A. niger, F.
oxysporum and A. flavus than the ligands. The octahedral structures (189 and 190, M =
Cd)
have been suggested for [CdLL'(H2O)] and [CdLL''(H2O)] respectively.
111
A DMF swollen suspension of polystyrene-anchored Schiff base, PSCH2LH2 (33;
R = 3-PSCH2OCO, X = O) upon refluxing with Cd(OAc)22H2O produces[9] a lightyellow, four-coordinate compound, [PSCH2LCd(DMF)]. The dibasic tridentate Schiff
base is coordinated to the metal ion through its phenolic O, azomethine N and enolic O
atoms. The furanyl O atom does not participate towards coordination.
Kumar et al.[10] have synthesized a yellow, polystyrene-anchored four-coordinate
compound, [PSCH2LHCd(DMF)] (where PSCH2LH3 = 34) by refluxing a DMF swollen
suspension of PSCH2LH3 and a DMF solution of Cd(OAc)22H2O. The PRC of the
compound is 53.8 and the MBC of PSCH2LH3 is 0.36 mmol of Cd per g of the ligand.
PSCH2LH3 behaves as a dibasic tridentate ONO donor ligand. DMF molecules are
coordinated to Cd as indicated by the decrease of (C==O) stretch of DMF from 1680 cm1
to 1645 cm-1.
A white, six-coordinate, non-electrolyte (M = 9.9 mho cm2 mol-1 in DMSO),
[CdCl2(LH)(H2O)]n (here LH = 84; R = H, R' = Me) has been synthesized by refluxing an

H2O/EtOH solution of CdCl2H2O and LH in 1:1 molar ratio for 1 h[56]. It is insoluble in
Me2CO, CHCl3 and C6H6 but is fairly soluble in DMF and DMSO. It melts between 220222 oC. LH acts as neutral tridentate ONN donor. The coordination compound shows
higher antibacterial activity against E. coli than LH, whereas its antifungal activity against
A. niger is less than LH. An octahedral polymeric structure (99, M = Cd) has been
assigned to the coordination compound.
A MeOH solution of Cd(OAc)22H2O on stirring with a MeOH solution of LH
(115)
gives a red coloured cubic crystals of a binuclear complex, [Cd2L2(OAc)2
(H2O)2][89]. The IR data are indicative of the involvement of phenolic O, azomethine N

and py N atoms towards coordination. The complex exhibits (CdO) and (CdN)
vibrations at 378 and 456 cm-1 respectively. The magnitude of as(OAc) and s(OAc)
stretches occurring at 1560 and 1416 cm-1 respectively in the complex indicates the
bidentate bridging coordination mode. The single crystal structure of the complex reveals
formation of 1:1 bridged binuclear complex in which both cadmium centers being sevencoordinate. The coordination around each Cd(II) is distorted monocapped octahedron via
N2O5 donor sites Its equatorial plane is occupied by two N atoms (pyridine N and imine N
) from the Schiff base and two bridging phenolic O atoms, whereas, axial positions are
112
described by one O atom from acetato group and O atom from H2O molecule. The
complex crystallizes in a triclinic fashion with a = 7.438 , b = 9.440 , c = 11.895 ,
= 1006.38o, = 97.78 = 113.01o and Z = 1. The fluorescence quantum yield of the
compound is higher than the ligand.
The synthesis of an air-stable, four-coordinate, non-electrolyte, [CdCl(LH)]4H2O
(here LH2 = 39) has been reported[13]. It is soluble in DMSO and DMF and slightly soluble
in MeCN. The ligand behaves as a monobasic tridentate OON donor. The carboxylato
group coordinates in a monodentate fashion. The (CdN) stretch occurs at 450 cm-1. The
coordination compound shows higher activity than the ligand against S. aureus, P.
mirabilis, K. pneumoniae, S. enteriditis and E. coli, while it remains inactive towards P.
aeruginosa. A tetrahedral structure (40, M = Cd) has been assigned to it.
An H2O/MeOH solution of CdCl2H2O on refluxing with a MeOH solution of
LH2 (116; R = R' = H) for h in the presence of AcONa forms[90] 1:1 dimeric, fourcoordinate compound, [CdL]2. The synthesis of the py adduct of the latter, [CdL(py)] has
also been reported. The coordination compound and its adduct are air-stable. They are
non-electrolytes in DMF. [CdL]2 is insoluble in CHCl3, MeOH, EtOH and C6H6 on the
other hand, [CdL(py)] is fairly soluble in CHCl3, dioxane, C6H6 and DMF. The
insolubility of the coordination compound in non-polar solvents indicates its dimeric or
polymeric nature. The IR data indicate the dibasic tridentate ONS donor nature of the
ligand.
An aqueous solution of Cd(OAc)22H2O reacts[22] with an EtOH solution of LH2
(48) in 1:2 molar ratio and forms an air-stable, pale-yellow, six-coordinate compound,
[Cd(LH)2]. The latter decomposes at 186 oC. It is insoluble in EtOH, C6H6 and CHCl3 but
is soluble in Me2CO, DMF and DMSO. It is non-electrolyte (M = 11.5 mho cm2 mol-1 in
DMSO and 2.1 mho cm2 mol-1 in Me2CO). The Schiff base acts as a monobasic tridentate
ligand coordinating through its hydroxylic O, azomethine N and thiolato S atoms. The
(CdN) vibrations occur at 565 cm-1. An octahedral structure (49, M = Cd) has been
suggested for it.
Shashidhara et al.[278] have synthesized the orange dimeric, four-coordinate
compounds, [CdL]2 (where LH2 = 191; R = H, Et, 1-Pr) by reacting an EtOH solution of
LH2 and CdCl2 2H2O in 1:1 molar ratio in the presence of AcONa. They are soluble in
113
DMF and DMSO. LH2 acts as a dibasic tridentate ONS donor ligand. The coordination
compounds exhibit the (CdO), (CdN) and (CdS) vibrations in the regions: 510520, 410-440 and 360-380 cm-1 respectively. The coordination compounds are weakly to
moderately active against E. coli, B. cirroflagelloscus, A. niger and C. albicans. The
ligands and their coordination compounds are less active than the standards
(cotrimoxazole and flucanazole).
An air-stable, four-coordinate, non-electrolyte (in DMSO), [CdCl(LH)] (where
LH2 = 50; R = OMe, R' = NH2) has been synthesized by stirring a MeOH solution of
NaLH and CdCl22H2O in 2:1 molar ratio for 8 h at room temperature[43]. It is soluble in
DMF and DMSO and slightly soluble in MeCN. The carboxylato group coordinates in a
monodentate fashion. NaLH behaves as a monobasic tridentate OOS donor ligand. The
presence of (MS) stretch at 300 cm-1 in the compound indicates coordination through S
atom of thiophene moiety. The compound shows lesser bactericidal activity than LH2
against S. aureus, E. faecalis, E. coli, P. mirabilis, S. sonnei and S. enteritidis. A distorted
tetrahedral structure [51; R = OMe, R' = NH2, A = nil, M = Cd] has been assigned to it.
A six-coordinate compound, [Cd(LH)2]4H2O (where LH2 = penicillin) has been
synthesized by stirring an aqueous solution of sodium penicillinate and CdCl22H2O in 1:1
molar ratio for 1 h at room temperature[91]. LH2 behaves as a monobasic tridentate OOO
donor ligand. An octahedral structure (117; M = Cd, x = 4) has been assigned to it.
A yellow, four-coordinate, non-electrolyte, [Cd(OAc)L]H2O (where LH = 52; R =
(C9H6N)CH, R' = NH2, X = Se) is obtained by stirring an EtOH solution of
Cd(OAc)22H2O and LH in 1:1 molar ratio for 1 h[279]. The IR data indicate a monobasic
tridentate NNSe donor behaviour of the ligand. The coordination sites are quinoline N,
azomethine N and Se atoms.
D.

An air-stable, four-coordinate compound, [CdL] (where LH2 = 55) is obtained by
refluxing a MeOH solution of Cd(OAc)22H2O and a CH2Cl2 solution of LH2 in 1:1 molar
MeOH and EtOH and insoluble in non-polar solvents. LH2 acts as a dibasic tetradentate
ONNO donor ligand.
114
Kumar et al.[25] have synthesized a light-yellow, four-coordinate compound,
[PSCH2LCd] [here PSCH2LH2 = 53; R = R' = Me, R'' = (CH2)2]. The dibasic ligand is
coordinated through its phenolic O, azomethine N and enolic O atoms.
Mononuclear and polynuclear coordination compounds, [Cd(LH3)(H2O)2] and
[Cd2(LH)(H2O)2]n of symmetrical, potentially heptadentate and tetracompartmental Schiff
base, N,N'-bis(3-hydroxysalicylidene)-1,3-diamino-2-propanol (LH5 = 192) have been
reported by Sanmartin
and coworkers[280]. The Schiff base behaves as a dibasic
tetradentate ONNO donor ligand. An octahedral structure for mononuclear compound with
Schiff base in equatorial position and H2O molecules at axial position has been suggested.
Tarafder et al.[281] have synthesized a yellow compound, [CdL] (where LH2 = 193;
R = SCH2Ph) by reacting CdBr24H2O and LH2 in the presence of KOH. The Schiff base
acts as a dibasic tetradentate SNNS donor ligand. The compound is better antibacterial
than the ligand against P. aeroginosa and B. cereus. The increased conjugation along with
the availability of a number of N and S nucleophilic sites in the coordination compound
contributes to the increased antimicrobial activity.
A yellow, four-coordinate compound, [Cd(LH2)]Cl2 (where LH2 = 194) has been
synthesized[282] by refluxing an EtOH solution of CdCl2H2O and LH2. The latter acts as
a neutral tetradentate N4 donor ligand. The compound exhibits better antimicrobial activity
than the ligand.
E.

Relatively little work has been reported on Cd(II) coordination compounds with
pentadentate ligands. An air-stable, seven-coordinate, monomeric, 1:1 electrolyte (M =

47.7 mho cm2 mol-1 in DMF), [Cd(NO3)2(LH2)] (here LH2 = neutral pentadentate SNNNS
donor ligand, 64; R = H, R' = Me) has been synthesized by refluxing Cd(NO3)24H2O and
LH2 in 1:1 molar ratio for 1 h[133]. The (C==N)(azomethine) and the (C==S) stretches of
LH2 occurring at 1646 and 894 cm-1 shift to 636 and 882 cm-1 respectively in the
coordination compound. The appearance of two new bands one at 1493 cm-1 and other at
1298 cm-1 indicates the monodentate coordination mode of nitrato group. The Cd(II) ion is
ligated to py N, two imine N and two thione S atoms of the ligand. The two axially
coordinated monodentate nitrato groups complete the seven-coordinate geometry. The
coordination compound displays an additional S M charge transfer band at 22222 cm-1
115
lending support to the coordinated mode of thione S atoms. It crystallizes in a triclinic
mode with a = 8.01 , b = 9.40 , c = 14.57 , = 103.7o, = 92.39o, = 100.65o, V =
1043.2 3 and Z = 2. A distorted pentagonal-bipyramidal geometry has been suggested for
it.
A black, monomeric, six-coordinate, 1:1 electrolyte (M = 46.82 mho cm2 mol-1),
[CdCl(LH4)]Cl3H2O (where LH4 = 195; R = Me, R' = CH2SH) is obtained[283] by reacting
CdCl2H2O and LH4 in CHCl3. It is soluble in DMF and DMSO and decomposes when
heated above 300 oC. The Schiff base acts as a neutral pentadentate SNNNS ligand
coordinating through its two azomethine N, pyridine N and two thione S atoms.
An air-stable, five-coordinate compound, [Cd(LH)]3H2O (where Na2LH = 62) has
been synthesized by stirring a MeOH solution of Na2LH and CdCl24H2O in 1:1 molar
ratio for 1 h at room temperature[35]. It is insoluble in H2O, EtOH, C6H6, Me2CO, MeCN,
Et2O, py, DMF and DMSO suggesting its polymeric nature. The non-coordinated H2O
molecules are lost between 80-110 oC. The O atom of -lactam is involved towards
coordination. The carboxylato group is coordinated in a monodentate fasion. Na2LH
behaves as a dibasic pentadentate ONOON donor ligand. The (CdN) stretch occurs at
~450 cm-1. The compound shows higher bactericidal activity than Na2LH against S.
sonnei, P. mirabilis and P. aeruginosa; lesser activity than the ligand against S. aureus and
S. enteritidis. A five-coordinate structure (63; M = Cd) has been assigned to it.
F.

The syntheses of a monomeric, six-coordinate compound, [CdL] [here LH2 = 66; R
2-OHC6H4
and
another
monomeric,
eight-coordinate,
[Cd(NO3)L'](ClO4) [here L' = 66; R = 2-C5H4N] have been reported
1:1
electrolyte,
[37,284]
. LH2 acts as a
dibasic hexadentate ON4O donor ligand, on the other hand, L' acts as a neutral hexadentate
N6 donor ligand in [Cd(NO3)L'](ClO4). In the latter coordination compound, the Cd(II) ion
is coordinated to three py and three asymmetric tripodal amine N atoms. The nitrato group
is coordinated in a bidentate mode. The Cd(II) ion is in a distorted dodecahedron
environment.
The compounds containing 1,10-phenanthroline moieties are known to be used as
fluorescent materials[285]. Niu et al. [286] have reported the syntheses of a brown complex,
[Cd)(dca)2(LH4]0.5H2O (here LH4 = 196, dca = dicynamide) and another yellow
116
[Cd(SCN)2(LH4)]CHCl3DMF. LH4 behaves as a neutral hexadentate O2N4 donor
coordinating through its carbonyl O, azomethine N and ring N atoms. Both the compounds
crystallize in a monoclinic fashion with a = 10.91, 9.85 , b = 18.14, 16.41 , c = 16.31,
24.22 , = = 90.0o, = 101.54, 96.28 and Z = 4, respectively. In both compounds, the
equatorial positions are occupied by four N atoms and two carbonyl O atoms of the ligand.
Two N atoms from two dca anions in brown complex, one N and one S atoms from
thiocynato groups in yellow compound occupy the apical positions. A hexagonal
bipyramidal geometry has been suggested for the complexes.
Niu et al.[287] have synthesized a monomeric, eight-coordinate compound,
[Cd(SCN)2(LH2)] (here LH2 = 197). It remains stable up to 300 C. LH2 behaves as a
neutral hexadentate ON4O donor ligand. The Cd(II) ion is coordinated to four N atoms and
two O atoms of the ligand. The thiocyanato groups are coordinated to the metal ion
through their N atoms in the coordination compound. The latter crystallizes in a
monoclinic mode. A distorted hexagonal-bipyramidal geometry has been suggested for it.
CHAPTER-1
117
COORDINATION COMPOUNDS OF SCHIFF BASE CONTAINING

UREA MOIETY
ABSTRACT
A MeOH solution of salicylaldehyde and ohydroxyphenylurea in 1:1 molar ratio
reacts and forms the Schiff base, LH3 (1). A MeOH solution of the latter reacts with
Zn(II), Co(II), Ni(II), Fe(III) and Zr(OH)2(IV) ions in 1:1 molar ratio and forms the
corresponding coordination compounds, [Zn(LH)(MeOH)] (2), [M(LH)(MeOH)2]2 (3, M =
Co, Ni), [FeCl(LH)(MeOH)]2 (4) and [Zr(OH)2(LH)(MeOH)2] (5). The coordination
compounds have been characterized on the basis of elemental analyses, molecular weight,
molar conductance, spectral (IR, reflectance, NMR) studies, thermo-gravimetric analyses
and magnetic susceptibility measurements. 1 acts as a dibasic tridentate ONO donor ligand
in 2-5.
The coordination compounds, 3 and 4 are paramagnetic, while 2 and 5 are
diamagnetic. A tetrahedral geometry to 2, an octahedral geometry to 3 and 4 and a

pentagonal-bipyramidal geometry to 5 are assigned. The energy optimized structures, 6
and 7 for 1 and 2 respectively are proposed using the semiempirical ZINDO/1 quantum
mechanical calculations.
INTRODUCTION
The Schiff bases containing O and N donor atoms are known to play important role
in biological systems and represent interesting models[288]. The Schiff bases and their
coordination compounds have received considerable research interest because of the
interaction of donor sites present in these ligands giving the coordination compounds of
different geometry and properties[289]. The coordination compounds of Schiff bases have also
been studied extensively due to their various applications like catalysts, pharmaceutical
agents, anti-tumor, antifungal, antibacterial, antiviral, anticonvulsive, antifouling and as
corrosion inhibitors[290]. The molecular modeling has played an important role in the study
of ligands and their coordination compounds[291]. The coordination compounds of Cu(II),
Zr(IV), Ti(IV) and Sn(IV) ions with the isomeric Schiff base, 56 [R = 2-OH(C6H4CH), R'
= 2-OH(C6H4)] of 1 have been reported elsewhere[292]. In the present Chapter, we have
synthesized and characterized the coordination compounds of 1 with Zn(II), Co(II), Ni(II),
118
Fe(III) and Zr(OH)2(IV) ions. It is expected that the present coordination compounds may
find applications in biochemical, analytical and antimicrobial fields.
EXPERIMENTAL
Materials
The various chemicals and solvents obtained from the sources mentioned in
Appendix-2 were used as received for the syntheses.
The estimation of metal, elemental contents, spectral (IR, reflectance, 1H NMR)
studies, thermal and magnetic susceptibility measurements were carried out by the
methods described in Appendix-3.
Synthesis of o-hydroxyphenylurea (ohypu)
o-Aminophenol (10.9 g, 100 mmol) was dissolved in 20 mL of 1:1 HCl. To this
solution, urea (24.0 g, 400 mmol) in small quantity with constant stirring, distilled water
(30 mL), HCl (1 mL) and glacial acetic acid (1 mL) were added. The brown solution
obtained was refluxed on a water bath for 2 h. The light-brown compound separated out
on cooling was suction filtered, washed with distilled water and recystallised from 50%
EtOH and dried in vacuo over silica gel. Melting point = 154 oC, yield = 90%; anal.
[C7H8N2O2; found (calcd)%; C = 55.38(55.26), H = 5.32(5.26), N = 18.23(18.42); IR
bands (KBr): (NH) (3050 cm-1), (C==O)(carbonyl) (1655 cm-1), (NH2) (1630
1
cm-
) and (CO) (1520 cm-1).
Synthesis of 1
An EtOH solution (20 mL) of salicylaldehyde (12.2 g, 100 mmol) and an EtOH
solution (100 mL) of o-hydroxyphenylurea (15.2 g, 100 mmol) were refluxed on a water
bath for 1 h. The excess of solvent was evaporated and the mixture was allowed to stand at
room temperature. The brown compound separated out was suction filtered, washed with
and recrystallized from EtOH and then dried as mentioned above. Melting point = 162 oC,
yield = 70%; anal. [C14H12N2O3; found (calcd.)%; C = 65.48(65.63), H = 4.85(4.69), N =
10.78(10.94); IR bands (KBr): (C==O)(carbonyl) (1665 cm-1), (C==N)(azomethine)
(1620 cm-1) and (CO) (1526 cm-1).
119
Synthesis of 2, 3 (M = Co, Ni)
A MeOH solution (30 mL) of appropriate metal acetate (5 mmol) was added while
constant stirring to a MeOH solution (100 mL) of 1 (1.28 g, 5 mmol). The solution was
refluxed on a water bath for 2-3 h. In order to stop the oxidation of Co(II) to Co(III), the
whole operation was carried out in N2 atmosphere. The solid residue obtained was suction
filtered, washed with MeOH and dried as mentioned above. Yield = 5070%.
Synthesis of 4
A MeOH solution (30 mL) of iron(III) chloride (anhydrous) (0.81 g, 5 mmol) was
added while constant stirring to a MeOH solution (100 mL) of 1 (1.28 g, 5 mmol). The
solution was refluxed for 3 h under anhydrous conditions and the brown solid obtained
was suction filtered, washed with MeOH and dried as mentioned above. Yield = 53%.
Synthesis of 5
A MeOH solution (50 mL) of freshly prepared HDAOHTZAc (5 mmol) was added
to a MeOH solution (50 mL) of 1 (1.28 g, 5 mmol). The mixture was refluxed for 3 h. A
MeOH solution (50 mL) of MeONa (0.54 g, 10 mmol) was added to the above mixture.
The yellow solid obtained was suction filtered, washed with MeOH and dried as
mentioned above. Yield = 70%.
RESULTS AND DISCUSSION

The
nucleophilic
addition
reacton
between
salicylaldehyde
and
o-
hydroxyphenylurea in EtOH in equimolar ratio followed by the elimination of one water

molecule results in the formation of LH3 (1) (Scheme 1). A MeOH solution of 1 reacts
with a MeOH solution Zn(II), Co(II), Ni(II), Fe(III) and Zr(OH)2(IV) ions in equimolar
ratio and forms 2-5 respectively. The formation of 2-5 takes place according to the
Scheme 2.
OH
C
H
H2 N C
N
H
[Scheme 1]
HO
O
EtOH
reflux
H2O
120
LH3 (1) + Zn(OAc)22H2O MeOH

[Zn(LH)(MeOH)] (2) + 2AcOH + 2H2O
Reflux
2LH3 (1) + 2M(OAc)24H2O MeOH

[M(LH)(MeOH)2]2 (3) + 4AcOH + 8H2O
Reflux
(M = Co, Ni)
2LH3 (1) + 2FeCl3 MeOH
[FeCl(LH)(MeOH)]2 (4) + 4HCl
Reflux
4LH3 (1) + [Zr4(OH)8(H2O)16](OAc)8 MeOH

4[Zr(OH)2(LH)(MeOH)2] (5) + 16H2O
Reflux
+ 8AcOH
[Scheme 2]
The complexes are insoluble in H2O, MeOH and EtOH but soluble in DMF and
DMSO. The experimental molar conductance values (4.58.2 mho cm2 mol-1 in 10-3 M
DMF solution) reveal their non-electrolytic nature (Table 1.1). The molecular weight
measurements indicate a dimeric nature of 3 and 4, while a monomeric nature of 2 and 5.
The coordination compounds, 2-5 do not lose weight on keeping in open air for hours
indicating that MeOH molecules are coordinated to metal ions. The coordinated MeOH
molecules are lost completely by heating 2-5 up to 120 oC.
Infrared spectral studies
The IR spectra of 1-5 were recorded in KBr (Table 1.2). 1 exhibits a strong band at
2700 cm1 due to the intramolecular Hbonded phenolic OH group (Fig. 1.1)[293]. The
coordination compounds exhibit a broad band at ~3400 cm-1 (Fig.1.2). This band may be
due to (i) coordinated MeOH molecule(s) in 2-5 and/or (ii) due to the enolization of LH2
during complexation[193]. 1 occurs in keto form as evident by the presence of a band at
1665
cm-1. The absence of this band and appearance of a new band at ~1240 cm-1 in 2-5
are indicative of enolisation during complexation and non-involvement of enolic O atom

towards coordination. The (C==N)(azomethine) stretch[294] of 1 occurs at 1620 cm1. On
complex formation, this band shifts to lower energy by 13-22 cm1 indicating
coordination[21] through azomethine N atom of 1. The (CO) stretch of 1 occurring at
121
1526 cm1 shifts to higher energy by 6 and 7 cm1 (<10 cm1) in 2 and 5 respectively and
by 20-35 cm-1 in 3 and 4 supporting the involvement of phenolic O atom towards
coordination[295]. The magnitude of the above shift of the (CO) stretch indicates a
monomeric structure for 2 and 5, and a dimeric structure for 3 and 4 as in the event of
dimeric structure, the (CO) stretch is known to shifts to higher energy by >10 cm-1.
The involvement of phenolic O and azomethine N atoms towards coordination is further
supported by the appearance of new non-ligand bands between 540-570 and 420-450 cm-1
due to the (MO) and (MN) vibrations in 2-5. These bands are in the expected order
of increasing energy: (MN) < (MO)[296] as expected due to the greater dipole
moment change in the MO vibration, greater electronegativity of the O atom than N
atom and shorter MO bond length than the MN bond length[297]. Thus, 1 behaves as a
dibasic tridentate ONO donor ligand in 2-5. The presence of a new band at 832 cm-1 in 4
due to the as(FeOFe) stretch supports the presence of an oxo-bridged structure in
it[298]. MeOH exhibits the (CO)(alcoholic) stretch[193] at 1034 cm1. This band shifts to
lower energy by 50-70 cm1 in 2-5 confirming the presence of coordinated MeOH[193]. The
absence of a new band between 825-960 cm1 in 5 rules out the presence of the (Zr==O)
stretch as well as the formulation of the compound as [ZrO(H2O)(LH)(MeOH)2]. The
presence of a new band at 1149 cm1 in the present compound indicates the presence of the
(ZrOH) bending mode[262] and this supports the formulation of this compound as
[Zr(OH)2(LH)(MeOH)2] and not as [ZrO(LH)(H2O)(MeOH)2]. Syamal and Kumar[200]
have developed a non-aqueous titration method for distinguishing the compounds
possessing [ZrO]2+ or [Zr(OH)2]2+ moiety. Oxozirconium(IV) compounds react with 3N
HCl in MeOH and as a result the oxo group gets protonated, while the zirconium(IV)
compounds
containing
[Zr(OH)2]2+
moiety
do
not
add
up
HCl
at
all.
[Zr(OH)2(LH)(MeOH)2] does not react with 3N HCl in MeOH and this conclusively
proves the absence of Zr==O bond in it.
Reflectance spectral studies
The nujol mull electronic spectra of 3 (M = Co, Ni) and 4 could not be recorded as
they do not form a good mull and hence their reflectance spectra were recorded (Table1.2). The coordination compound, 3 (where M = Co) shows three bands at 9210, 13550
and 19760 cm1 due to the 4T1g(F) 4T2g(F)(1), 4T1g(F) 4A2g(F)(2), 4T1g(F)
122
4
T1g(P)(3) transitions respectively, in an octahedral environment[297,299]. The spectral
parameters calculated by following the standard method[299,300] and using the free ion
Racah parameter (B) value[107] of 971 cm-1 are: 3:1 (2.14), 10Dq (10371 cm-1), B (780.7),
(0.80), Bo (19.5%) and CFSE (99.33 kJ mol-1). The coordination compound, 3 (when M
= Ni) exhibits three bands at 9720, 16390 and 25540 cm1 due to the 3A2g(F) 3T2g(F)(1),
3
A2g(F) 3T1g(P)(2) and
A2g(F) 3T1g(F)(3) transitions respectively, indicating an
octahedral geometry around Ni(II) ions[301]. The spectral parameters calculated by

following the standard method[301,302] and using the free ion Racah parameter (B) value[107]
of 1030 cm-1 are: 2:1 (1.69), 10Dq (9720 cm-1), B (799.8), (0.77), Bo (23%) and CSFE
(139.65 kJ mol-1). The reduction of Racah parameter [from the free ion values: 971 cm-1
to 780.7 cm-1 for Co(II) and from 1030 cm-1 to 799.8 cm-1 for Ni(II)] and the values of %
covalence in 3 [(19.5%, when M = Co(II) and 23.0%, when M = Ni(II)] are indicative of
the covalent nature of Co(II) and Ni(II) coordination compounds. The 10Dq value of the
Co(II) compound is greater than that of the corresponding Ni(II) compound:
[Co(LH)2(MeOH)2]2, 10371 cm-1 > [Ni(LH)2(MeOH)2]2, 9720 cm-1. This is in line with the
spectrochemical series of metal ions for a given ligand, given stoichiometry and a given
stereochemistry[302]: Co(II) > Ni(II). The B0 value of the Ni(II) compound is comparable to
that
of
the
corresponding
Co(II)
compound:
[Co(LH)2(MeOH)2]2,
19.5%
[Ni(LH)2(MeOH)2]2, 23%. This is in line with the nephelauxetic metal ion series in terms
of B and B0 for a given ligand, given stoichiometry and a given stereochemistry[302]. The
higher negative CFSE value in the Co(II) coordination compound in comparison to that of
the corresponding Ni(II) coordination compound is as expected. 4 exhibits three bands at
12000, 15650 and 19000 cm-1 corresponding to the 6A1g 4T1g(G), 6A1g 4T2g(G) and
6
A1g 4A1g(G) transitions respectively in an octahedral environment[25].
NMR Studies
The 1H NMR spectra of 1 and 2 have been recorded in DMSO-d6. The chemical
shifts () are expressed in ppm downfield from TMS[303]. 1 exhibits a multiplet at 6.828.00 ppm due to the aromatic protons, a singlet at 7.32 ppm due to the azomethine
proton, a broad signal at 10.91 ppm due to the phenolic proton and a singlet at 11.73
ppm due to the NH proton. MeOH exhibits the alcoholic proton at 4.84 ppm and
methyl protons at 3.35 ppm. The appearance of the signals due to the alcoholic proton
123
(singlet, 1H) at 2.74 ppm and methyl protons at 3.58 ppm in 2confirms the presence of
MeOH in 2. The signal due to the azomethine proton appears at 7.03 ppm. This
downward shift is indicative of coordination of N atom of >C==N group[178]. The
appearance of enolic proton at 13.5 ppm and absence of NH proton in 2 indicate the
enolization of the keto group during complex formation and non-involvement of enolic O
towards coordination.
Thermo-gravimetric analyses
The thermo-gravimetric analyses of 2 and 5 indicate that these compounds
decompose in two stages. A mass loss of 9.27% (calcd 9.11%) and 14.56% (calcd 14.44%)
between 80-120 oC, occurring in the above compounds indicates the loss of one and two
coordinated MeOH molecules respectively. A steep decrease in weight (between 250-600
o
C) attributes to the decomposition of organic skeleton. The plateau obtained after heating
the residue above 600 oC corresponds to the formation of metal oxides [ZnO (obsd =
23.48%, calcd = 23.16%) and ZrO2 (obsd = 27.52%, calcd = 23.8%)]. These values are in
accordance with the proposed formulae for these compounds.
Magnetic measurements
The experimental values (4.3 and 2.5 B.M.) of the magnetic moment for the
dimetallic
coordination
compounds,
[Co(LH)(MeOH)2]2
and
[Ni(LH)(MeOH)2]2
respectively are lower than the corresponding spin-only values[304]. These lower values are
due to the presence of an antiferromagnetic exchange between the two metal ions
connected by phenoxo bridges. The magnetic moment of 4 is 5.03 B.M. This value is also
lower than the expected value for high-spin d5 state (eff = 5.92 B. M.) and this indicates
the presence of an antiferromagnetic exchange interaction in 4. The lower value suggests
the dimerization through the phenolic O atom of LH3[107]. The coordination compounds of
Zn(II) and Zr(IV) are diamagnetic as expected.
Molecular modeling
The 3-D molecular modeling of 1 and 2 have been carried out using hyperchem
series of program[305]. The structures have been optimized using molecular mechanics and
semiempirical ZINDO/1 (Polak-Ribiere, RMS = 0.01 kcal).
The energy optimized
structures of 1 and 2 are presented in Figures 6 and 7 respectively. The computed

structural properties of the above compounds and their selected bond lengths and bond
124
angles are listed in Table 1.3. The model of 1 shows significantly short [C(7)==N(8), 1.32
] bond length indicating the double bond character between C and N atoms. Also, the
[C(5)C(7), 1.42 ], [C(13)O(21), 1.32 ] bond lengths are comparable to the
reported values[306]. The geometry optimized model of 2 possesses bond length [Zn(1)
O(2), 2.165 ] and bond angles [N(3)Zn(1)O(4), 100.3o], [O(2)Zn(1)N(3),
92.508o] comparable to those reported using X-ray crystallography[307].
CONCLUSION
The reaction of the dibasic tridentate ONO donor Schiff base (1) with Zn(II),
Co(II), Ni(II), Fe(III) and Zr(OH)2(IV) ions results in the formation of coordination
compounds with different geometries. [M(LH)(MeOH)]2 (3) (where M = Co, Ni) and
[FeCl(LH)(MeOH)]2 (4) are dimetallic having an octahedral geometry around the metal
ion.
[Zn(LH)(MeOH)]
(2)
is
monometallic
with
tetrahedral
geometry.
[Zr(OH)2(LH)(MeOH)2] (5) is monometallic with trigonal-bipyramidal geometry. The

coordination compounds of 1 are quite comparable to those of the isomeric Schiff base
derived from the condensation of salicylaldehyde and salicylhydrazide.
CHAPTER-2
125
LIGATIONAL BEHAVIOR OF THE AZETIDIN-2-ONE DERIVED

FROM SALICYLALDEHYDE AND O-HYDROXYPHENYLUREA
TOWARDS SOME DI-, TRI- AND HEXAVALENT METAL IONS
ABSTRACT
The cyclo-addition reaction of LH3 (1) with chloroacetyl chloride in the presence
of Et3N in dioxane affords the corresponding azetidin-2-one, L'H3 (8). The reaction of 8
with Cu(II), Cd(II), Mn(II), Fe(III) and MoO2(VI) ions in MeOH results in the formation
of corresponding coordination compounds, [Cu(OAc)(L'H2)] (9), [Cd(OAc)(L'H2)] (10),
[Mn(OAc)(L'H2)(MeOH)2]
(11),
[FeCl2(L'H2)(MeOH)]
(12)
and
[MoO2(acac)(L'H2)(MeOH)] (13). The compounds have been characterized on the basis of

elemental analyses, molecular weight, molar conductance, spectral (IR, reflactance, ESR)
and magnetic susceptibility measurements. 8 acts as a monobasic tridentate ONO donor
ligand in these monomeric compounds. A square-planar structure for 9, a tetrahedral
structure for 10 and an octahedral structure for 11 and 12 have been proposed. 13 affords
an eight-coordinate structure.
INTRODUCTION
The 2-carbonyl derivatives of azetidine containing a four-membered heterocyclic
ring with N as heteroatom, are known as azetidin-2-one or -lactam. They are most widely
used antibiotic, antimicrobial, anti-inflammatory, anticonvulsant and antitubercular
substances[308]. They also act as enzyme inhibitors and are effective on central nervous
system[309]. In view of the above importance of azetidin-2-one and in continuation of our
earlier work on the metal complexes of azetidin-2-one[310], the syntheses and
characterization of the coordination compounds of 8 with Cu(II), Cd(II), Mn(II), Fe(III)
and MoO2(VI) ions are presented in this Chapter.
EXPERIMENTAL
Materials
126

The estimation of metal, elemental contents, molar conductivity measurements,
spectral (IR, reflectance, ESR) studies and magnetic susceptibility measurements were
carried out by the methods described in Appendix-3.
Synthesis of 8
Chloroacetyl chloride (2.26 g, 20 mmol) was added drop wise during a period of 2
h to a continuously stirred dioxane solution (50 mL) of 1 (2.56 g, 10 mmol) in the
presence of Et3N (3.03 g, 30 mmol). Triethylamine hydrochloride formed was filtered off
and the volume of the filtrate was reduced to 50%. The solution was kept aside for 24 h
and the solid product formed was suction filtered, washed with dioxane, recrystallized
from CHCl3 and then dried as mentioned elsewhere. Yield = 30%; anal. [C16H13N2O4Cl;
found(calcd)%; C = 57.44(57.74), H = 3.82(3.91), N = 8.45(8.42), Cl = 10.43(10.68); IR
bands (KBr): (OH) (intramolecular H-bonding) (2765 cm-1), (C==O)(-lactam)(1728
cm-1), (C==O)(amide) (1670 cm-1), (CO) (1510 cm-1), (CN)(-lactam) (1410
cm-1) and (CCl)
(-lactam) (780 cm-1).
Syntheses of 9-13
A MeOH solution (30-50 mL) of appropriate metal acetate/chloride/complex (10
mmol) was added to a MeOH solution (50 mL) of 8 (3.32 g, 10 mmol). The solution was
refluxed for ~ 4 h on a water bath and the solid products obtained were suction filtered,
washed with MeOH and dried as mentioned above. Yield = 50-60%.

The Schiff base, sal-o-hydroxyphenylurea (1) undergoes cyclo-condensation
reaction with chloroacetyl chloride in dioxane in the presence of Et3N and forms 8
(Scheme 3). The reaction of the latter with appropriate metal ions in 1:1 molar ratio
produces the monomeric coordination compounds of the types, [Cu(OAc)(L'H2)] (9),
[Cd(OAc)(L'H2)] (10), [Mn(OAc)(L'H2)(MeOH)2] (11), [FeCl2(L'H2)(MeOH)] (12) and
[MoO2(acac)(L'H2)(MeOH)] (13). The formations of 9-13 takes place according to the
Scheme 4.
127
/
chloroacetyl chloride
Et3 N dioxane
L H3 (8 )
[Scheme 3]
LH3 (8) + Cu(OAc)2H2O MeOH
[Cu(OAc)(L'H2)] (9) + AcOH + H2O
Reflux
LH3 (8) + Cd(OAc)22H2O MeOH

[Cd(OAc)(L'H2)] (10) + AcOH + 2H2O
Reflux
LH3 (8) + Mn(OAc)24H2O MeOH

[Mn(OAc)(L'H2)(MeOH)2] (11) + AcOH + 4H2O
Reflux
LH3 (8) + FeCl3 MeOH

[FeCl2(L'H2)(MeOH)] (12) + HCl
Reflux
LH3 (8) + [MoO2(acac)2] MeOH

[MoO2(acac)(L'H2)(MeOH)] (13) + acacH
Reflux
[Scheme 4]
The coordination compounds are insoluble in common solvents such as H2O,
MeOH, EtOH but are soluble in DMF and DMSO. The experimental molar conductance
values (5.38.3 mho cm2 mol-1 in 10-3 M DMF solution) of these compounds are indicative
of their non-electrolytic nature. The analytical data of 8 and its coordination compounds
are presented in Table 2.1.
The IR spectra of 8-13 were recorded in KBr and the prominent peaks are
presented in Table 2.2. The Schiff base (1) (Fig.1.1) exhibits the (C==O)(carbonyl),
(C==N)(azomethine) and (CO) stretches at 1665, 1620 and 1526 cm-1 respectively.
The (C==N)(azomethine) stretch of 1 disappears in 8 (Fig.2.1) and a new band due to the
(CN)(-lactam) stretch appears at 1410 cm-1 supporting the formation of the
corresponding azetidin-2-one[311]. The formation of 8 is further supported by the
appearance of a new band at 1728 cm-1 and other at 780 cm-1 due to the (C==O)(lactam) and the (CCl)(-lactam) stretches respectively[312]. The (CO) stretch of 8
occurring at 1510 cm-1 shifts to higher energy by 10 cm-1 in 9-13 (Fig. 2.2) indicating the
involvement of phenolic O atom towards coordination. The magnitude of above shift of
the (CO) stretch indicates the monomeric nature of the present coordination
128
compounds. The molecular weight data also suggest their monomeric nature. 8 occurs in
keto form as evident by the presence of a band at 1670 cm-1 due to the (C==O)(amide)
stretch[91]. The persistence of this band at the same energy in 8 as well as in 9-13 indicates
the non-involvement of amide O atom towards coordination. The (C==O)(-lactam)
stretch of 8 occurring at 1728 cm-1 shifts to lower energy by 12-30 cm-1 indicating the
involvement of O atom of -lactam moiety towards coordination[313]. The Cl atom of the
-lactam ring does not participate in coordination as evident by the presence of the (C
Cl)(-lactam) stretch at the same energy in 8 and 9-13. The appearance of a broad band
between 3360-3440 cm-1 due to the (OH)(MeOH) stretch and the decrease of the (C
O) (MeOH) stretch from 1034 cm-1 to lower energy by 40-60 cm-1 in 11-13 indicates the
presence of coordinated MeOH molecule(s)[314]. The as(OAc) and s(OAc) stretches of
free acetate ions occur at 1560 and 1416 cm-1 respectively[25]. These bands occur between
1586-1595 and 1372-1380 cm-1 respectively in 9-11. The magnitude of energy separation
( = 211-223) between as(OAc) and s(OAc) stretches is >144 cm-1 which indicates the
monodentate nature[315] of acetato group in 9-11. The occurrence of two bands, one at
940 cm-1 and other at 880 cm-1 in 13, due to the s(O==Mo==O) and as(O==Mo==O)
stretches respectively, indicates the presence of a cis-MoO2 configuration in it[208].
Acetylacetone is coordinated here as a monobasic bidentate OO donor ligand as evident by
the presence of a band at 1695 cm-1 due to the (C==O) stretch[316]. The new non-ligand
bands in the present coordination compounds in the low frequency region are assigned as
(MO)(550-575 cm-1) and (MN)(430-465 cm-1) and these bands are in the expected
order of increasing energy: (MN) < (MO)[297].
The appearance of an asymmetric band at 17450 cm-1 due to the 2B1g 2A1g, 2B2g
and 2Eg transitions in 9 is consistent with the Cu(II) ion in a square-planar environment[30].
11 exhibits three bands at 16236, 23400 and 25570 cm-1 due to the 6A1g 4T1g(G)(1), 6A1g
T2g(G)(2) and
A1g
A1g(G)(3) transitions respectively in an octahedral
symmetry[300]. 12 exhibits three bands at 12500, 15000 and 19220 cm-1 corresponding to
the 6A1g 4T1g(G), 6A1g 4T2g(G) and 6A1g 4A1g(G) transitions respectively in
octahedral symmetry [300].
129
ESR spectral studies
The X-band ESR spectrum of 9 (Fig.2.3) shows usual anisotropic pattern with two
g values, hich are characteristic of tetragonal type symmetry. Its spin Hamiltonian
parameters are: All = 1.50 10-2 cm-1, A = 3.0 10-3 cm-1, g|| = 2.8, g= 2.08, = 0.49, G
= 3.50, Pd = 1.54 10-2 cm-1, Pd = 7.55 10-2 cm-1, 2Cu = 0.77 and (')2 = 0.33. The
pattern g|| > g > 2 is suggestive of dx2-y2 ground state. The value of g|| (2.28) indicates the
covalent character in the metal-ligand bonding. The value of G (3.50) is indicative of
strong field nature of the ligand in the complex. The values of 2Cu (0.77) and (')2 (0.33)
indicate the covalent nature of 9. The positive value of (0.49) suggests that All should be
.greater
than A. The Pd value (1.54 10-2 cm-1) is lower than free ion value (3.5 10-2
cm-1), which is suggestive of the presence of the covalent character between metal-ligand
bonding. The absence of a band at ~1500 gauss due to Ms = 2 transition in 9 rules out the
presence of CuCu interaction.
The room temperature magnetic moments of the compounds are presented in Table
2.2. The Cu(II) ion belongs to S = system and since its spin-orbit coupling constant is
negative, the magnetically dilute Cu(II) compounds, due to the presence of orbital
contribution are expected to exhibit magnetic moments higher than the spin-only value
(1.73 B.M.). The magnetic moment of 9 is 1.87 B.M. in the range expected for the
monomeric Cu(II) compounds. The magnetic moment of 11 is 5.81 B.M., which lies in the
normal range reported for the magnetically dilute octahedral compounds of Mn(II) ions[107]
The magnetic moment of 12 is 5.78 B.M. suggesting a high-spin octahedral environment
around Fe(III) ion in the complex[317]. The coordination compounds of Cd(II) and
MoO2(VI) ions are diamagnetic as expected.
CONCLUSION
On the basis of analytical data, valence requirements and spectral studies, it is
proposed that 8 behaves as a monobasic tridentate ONO donor ligand in these monomeic
and non-electrolyte coordination compounds. The data suggest a square-planar structure
for 9, a tetrahedral structure for 10, an octahedral structure for 11 and 12. The compound,
13 is eight-coordinate.
CHAPTER-3
130
PHYSICO-CHEMICAL STUDIES ON THE COORDINATION

COMPOUNDS OF THIAZOLIDIN-4-ONE DERIVED FROM
SALICYLALDEHYDE AND O-HYDROXYPHENYLUREA
ABSTRACT
The Schiff base, LH3 (1) undergoes cyclo-addition reaction with merceptoacetic
acid in dry C6H6 and forms the corresponding thiazolidin-4-one, L'H3 (14). A MeOH
solution of 14 reacts with Cu(II), Co(II), Ni(II), MoO2(VI) and Zr(OH)2(IV) ions and
forms the monomeric, non-electrolyte coordination compounds, [Cu(OAc)(L'H2)] (15),
[M(OAc)(L'H2)(MeOH)2] (16) (here M = Co, Ni), [MoO2(acac)(L'H2)(MeOH)] (17) and
[Zr(OH)3(L'H2)] (18). The coordination compounds have been characterized on the basis
of elemental analyses, molecular weight, molar conductance, spectral (IR, reflectance,
NMR) studies and magnetic susceptibility measurements. 14 behaves as a monobasic
tridentate ONO donor ligand in these coordination compounds. A square-planar structure
for 15, an octahedral structure for 16 (M = Co, Ni) and 18 and an eight-coordinate
structure for 17 are suggested.
INTRODUCTION
Thiazolidin-4-ones belong to an important group of heterocyclic compounds with
carbonyl group at fourth position[318]. They show broad spectrum of biological activities
due to their ready accessibility and diverse chemical reactivity[319]. They are involved in
variety of applications such as antimicrobial, antibacterial, anticonvulsant, antifungal, antiHIV, antiproliferative, anti-inflammatory, cystic fibrosis and antithyroid[320-322] etc. Many
drugs possess modified pharmacological properties in the form of the coordination
compounds[323]. These facts prompted us to explore the coordination behavior of
thiazolidin-4-one (14) towards Cu(II), Co(II), Ni(II), MoO2(VI) and Zr(OH)2(IV) ions.
EXPERIMENTAL
Materials
131
The estimation of metal, elemental contents, spectral (IR, reflectance, 1H NMR)
studies and magnetic susceptibility measurements were carried out by the methods
described in Appendix-3.
Synthesis of 14
A dry C6H6 solution of 1 (2.56 g, 10 mmol) and mercaptoacetic acid (0.92 g, 10
mmol) were refluxed for 12 h on a water bath. The mixture was cooled to room
temperature and then was washed with 10% NaHCO3 solution. C6H6 layer was separated
using a separating funnel. The partial evaporation of C6H6 layer gave a solid product,
which was filtered, washed with and recrystallized from petroleum ether (b. pt. = 40-60
o
C). The compound was dried as mentioned elsewhere. Yield = 15%, anal. [C16H14N2O4S;
found(calcd)%; C = 58.67(58.18), H = 4.36(4.24), N = 8.35(8.48), S = 9.57(9.70)]; IR

bands (KBr): (OH)(intramolecular H-bonding) (2870 cm-1), (C==O)(thiazolidinone
ring) (1710 cm-1), (C==O)(amide) (1665 cm-1), (CN)(thiazolidinone ring) (1575 cm1
), (CO) (1528 cm-1) and (CS) (thiazolidinone ring) (832 cm-1).
Syntheses of 15-18
A MeOH solution (30-50 mL) of the appropriate metal salt (5 mmol) was added to
a MeOH solution (50 mL) of 14 (1.65 g, 5 mmol) and the mixture was then refluxed for 34 h. The solid products formed were suction filtered, washed repeatedly with MeOH and
were then dried as mentioned elsewhere. Yield = 50-65%.

The cyclo-addition reaction of the Schiff base, LH3 (1) with merceptoacetic acid in
dry C6H6 results in the formation of L'H3 (14) (Scheme 5). The reaction of a MeOH solution
of 14 with appropriate metal salts in 1:1 molar ratio under reflux produces respective air-
dry C 6H
6
Reflux
[Scheme 5]
L H3 14
HSCH2 COOH
(
LH 3 1
stable coordination compounds, 15-18. The formation of 15-18 takes place as per Scheme 6.
132
Cu(OAc)2H2O + L'H3 (14) MeOH

[Cu(OAc)(L'H2)] (15) + AcOH + H2O
Reflux
M(OAc)24H2O + L'H3 (14) MeOH

[M(OAc)(L'H2)(MeOH)2] (16) + AcOH + 4H2O
Reflux
(M = Co, Ni)
[MoO2(acac)2] + L'H3 (14) MeOH
[MoO2(acac)(L'H2)(MeOH)] (17) + acacH
Reflux
[Zr4(OH)8(H2O)16](OAc)8 + 4L'H3 (14) MeOH

4[Zr(OH)3(L'H2)] (18) + 12H2O
Reflux
+ 8AcOH
[Scheme 6]
The coordination compounds, 16 (M = Co, Ni) and 17 do not lose weight on
heating at 120 oC for hours, indicating that MeOH molecule(s) are not lost but are
coordinated to metal ion. They are insoluble in H2O, MeOH, EtOH and soluble in DMSO
and DMF. Their experimental molar conductance values (M = 4.3-9.6 mho cm2 mol-1 in
10-3 DMF solution) (Table 3.1) indicate their non-electrolytic nature[324].
The IR spectra of 1, 14-18 were recorded in KBr and the important peaks are
presented in Table 3.2. 1 (Fig 1.1) exhibits the (C==O)(carbonyl), (C==N)(azomethine)
and (CO) stretches at 1665, 1620 and 1526 cm-1 respectively. The disappearance of
the (C==N)(azomethine) stretch (1620 cm-1) of 1 and the appearance of a new band at
1575 cm-1 due to the (CN) (thiazolidinone ring) stretch[325] in 14 suggests the formation
of the corresponding thiazolidin-4-one (Fig.3.1). The formation of 14 is further supported
by the appearance of a new band at 832 cm-1 due to the (CS)(thiazolidinone ring)
stretch[226]. Both these bands remain
unchanged
in the coordination compounds
indicating the non-involvement of both N and S atoms of thiazolidin-4-one moiety

towards the coordination. The (C==O)(thiazolidinone ring) stretch[326] occurring at 1710
cm-1 in 14 undergoes a negative shift by 30-38 cm-1 in 15-18 (Fig.3.2) indicating the
coordination through carbonyl O atom of thiazolidin-4-one moiety. 14 occurs in the keto
form as evident by the presence of a strong band at 1665 cm-1 due to the (C==O)(amide)
133
stretch[294]. This band remains almost at the same energy in 15-18, which rules out the
involvement of keto O atom towards coordination. The strong band occurring at 2870 cm-1
in 14 due to the intramolecular H-bonded OH group of the phenolic moiety disappears in
15-18 indicating the breakdown of H-bonding and the subsequent deprotonation of OH
group followed by the involvement of phenolic O atom towards coordination[198]. The
(CO) stretch of 14 occurring at 1528 cm-1 undergoes a positive shift by 10 cm-1 in
15-18 and thus supports the involvement of phenolic O atom towards coordination[182].
The magnitude of the above shift of the (CO) stretch supports the monomeric
structures of 15-18. The experimental molecular weight data also support the same (Table
3.1). The free acetate ion exihibits as(OAc) and s(OAc) stretches at 1560 cm-1 and 1416
cm-1 respectively[296]. On complexation, the former band undergoes a positive shift and the
latter to a negative shift. The appearance of two new bands between 1564-1572 cm-1
[as(OAc)] and 1340-1352 cm-1 [s(OAc)] stretches indicates the presence of the
coordinated acetato group in 15 and 16 (M = Co, Ni). The energy difference ( = 220225 cm-1) between these stretches is >210 cm-1 which indicates the monodentate nature of
the carboxylato moiety. The presence of a broad band between 3345-3435 cm-1 due to the
(OH)(MeOH) stretch and the decrease of the (CO)(MeOH) stretch[296] from 1034
cm-1 to lower energy by 62-68 cm-1 respectively in 16 (M = Co, Ni) and 17 indicates the
presence of coordinated MeOH molecule(s). The appearance of new bands at 945 and 914
cm-1 due to the s(O==Mo==O) and as(O==Mo==O) stretches respectively, in 17
indicates the presence of a cis-MoO2 structure[262] in 17. The appearance of two new
bands, one at 1578 cm-1 and other at 1395 cm-1 due to the s(CO) and as(CO)
stretches
respectively in 17 suggests the presence of coordinated acac group in a
monobasic bidentate manner [316]. The absence of a new band between 850-950 cm-1, due
to the (Zr==O) stretch favours the formulation of 18 as [Zr(OH)3(LH2)] and not as
[ZrO(OH)(L'H2)(H2O)]. The presence of a broad band between 3400-3450 cm-1 and the
appearance of a new band at 1135 cm-1 due to the (ZrOH) bending mode also support
the proposed structures of the present Zr(OH)2(IV)compound[327].
The reflectance spectrum of 15 (Table3.2) exhibits an asymmetric broad band at
17300 cm-1 due to the 2B1g 2A1g, 2B2g and 2Eg transition suggesting a square-planar
134
geometry (Fig.3.3) [7]. The absence of a band in the range 8000-10000 cm-1 precludes the
presence of a tetrahedral structure[7]. 16 (M = Co) exhibits three bands at 8650, 17340 and
19500 cm-1 due to the 4T1g(F) 4T2g(F)(1), 4T1g(F) 4A2g(F)(2), 4T1g(F) 4T1g(P)(3)
transitions respectively in an octahedral symmetry[300]. The 3/1 value in the present
compound is 2.25 and it lies in the usual range (2.0-2.8) reported for majority of
octahedral Co(II) compounds[300]. The spectral parameters are: 10Dq = 9786.9 cm-1, B =
799.1, = 0.82, 0 = 18.0% and LFSE = 93.7 kJ mol-1. The appearance of three bands at
8670, 15860 and 24500 cm-1 in 16 (M = Ni) due to the 3A2g(F) 3T2g(F)(1), 3A2g(F)
3
T1g(P)(2) and 3A2g(F) 3T1g(F)(3) transitions respectively support an octahedral
symmetry[300]. The 2/1 value in the present compound is 1.83, which occurs in the usual
range (1.6-1.83) reported for the majority of octahedral Ni(II) compounds[107]. The spectral
parameters are: 10Dq = 8670 cm-1, B = 849.6 cm-1, = 0.82 and 0 = 18.0% and LFSE =
124.56 kJ mol-1. The reduction of Racah parameter [from the free ion values: 971 to 799.1
cm-1 for Co(II) and from 1030 to 849.6 cm-1 for Ni(II)] and the values of % covalence
(18.0) in 16 (M = Co, Ni) are indicative of the covalent nature of Co(II) and Ni(II)
coordination compounds[107].
NMR spectral studies
The 1H NMR spectra of 1, 14 and 18 have been recorded in DMSO-d6. The
chemical shifts () are expressed in ppm from TMS[303]. The important signals occurring in
1 at 6.82-8.00, 7.32, 10.91 and 11.7 ppm are due to the aromatic (m, 8H), azomethine (s,
1H), OH (d, 2H) and NH (s, 1H) respectively[328]. The disappearance of azomethine
signal ( 7.32 ppm) and the appearance of new signals at 5.89 and 3.83 ppm due to the
CHNS (s, 1H) and >CH2 (d, 2H) protons[329] respectively support the formation of 14. The
signals due to the NH and phenolic OH protons occur at 11.54 and 10.72 ppm
respectively in 14. The presence of the signal at 10.83 ppm (1H) in 18 suggests that one
of the phenolic OH groups of 14 is involved in coordination and other remains free. Due to
the lack of X-ray crystal study, we are unable to suggest which of the phenolic OH groups
is involved in coordination. However, on the basis of steric hindrance, we suggest that the
phenolic OH group near to the thiazolidine moiety is not involved in coordination. The
appearance of NH proton at 11.48 ppm in 18 indicates the presence of keto form of
14[330]. The other signals in 18 occurring at 3.8 and 5.82 ppm are due to the >CH2 and
135
CHNS protons respectively. The presence of multiplet in the range 6.48-7.45 ppm is due
to the aromatic protons[328] in 14 and 18.
The observed value (1.82 B.M.) of the magnetic moment of 15 is higher than the
spin-only value (1.73 B.M.) due to the presence of orbital contribution[112]. This value lies
in the usual range (1.75-2.20) reported for the magnetically dilute Cu(II) compounds[107].
The magnetic moments of 16 (M = Co, Ni) are 4.78 and 3.32 B.M. respectively, consistent
with high-spin octahedral structure[107]. The coordination compounds, 17 and 18 are
diamagnetic as expected.
CONCLUSION
On the basis of above findings (analytical data, valance requirements, conductance
measurements, molecular weight, spectral, magnetic susceptibility measurements), it is
proposed that 14 acts as a monobasic tridentate ONO donor ligand in 15-18. We propose a
square-planar structure for 15, an octahedral structure for 16 (M = Co, Ni) and 18, and an
eight-coordinate structure for 17.
CHAPTER-4
136
STUDIES ON THE COORDINATION COMPOUNDS OF THE

POLYSTYRENE-ANCHORED SCHIFF BASE OBTAINED
FROM THE CONDENSATION OF CHLOROMETHYLATED
POLYSTYRENE, 3-FORMYLSALICYLIC ACID AND oHYDROXYPHENYLUREA
ABSTRACT
Chloromethylated polystyrene (PSCH2Cl) reacts with 3-formylsalicylic acid and
forms polystyrene 3-formylsalicylate. The nucleophilic addition reaction followed by the
elimination of one water molecule between polystyrene-3-formylsalicylate and ohydroxyphenylurea in DMF in the presence of ethyl acetate results in the formation of
polystyrene-anchored Schiff base, PSCH2LH3 (19). The polystyrene-anchored
coordination compounds of the types, [PSCH2LH2Cu(OAc)(DMF)] (20), [PSCH2
LH2Cd(OAc)(DMF)]
(21),
[PSCH2LH2Mn(OAc)(DMF)3]
(22),
[PSCH2
LH2FeCl2(DMF)2] (23) and [PSCH2LH2MoO2(acac)] (24) (acacH = pentane-2,4-dione)

have been synthesized by refluxing a DMF swollen suspension of 19 and appropriate
metal salts/compound. The polystyrene-anchored coordination compounds have been
characterized on the basis of elemental analyses, spectral (IR, reflactance, ESR) and
magnetic susceptibility measurements. 19 behaves as a monobasic bidentate ON donor
ligand in these coordination compounds. [PSCH2LH2Cu(OAc)(DMF)] (20) is squareplanar and paramagnetic, [PSCH2LH2Cd(OAc)(DMF)] (21) is tetrahedral and
diamagnetic. The paramagnetic compounds (22 and 23) and the diamagnetic compound
(24) have attained an octahedral geometry.
INTRODUCTION
The functionalized polymers and their coordination compounds are known to
exhibit the chelating abilities[331], catalytic activity[332,333] selectivity, efficiency,
operational flexibility and stability[334,335]. A perusal of the literature indicates that a
number
of
polymer-anchored
ligands
containing
oxygen
atom(s)
have
been
reported[162,336], however, there is no report on the coordination compounds of polymeranchored ligands containing urea moiety. In view of their pronounced coordinating
properties, we have synthesized and characterized the polystyrene-anchored Schiff base,
137
PSCH2-LH3 (19) and its coordination compounds with Cu(II), Cd(II), Mn(II), Fe(III) and
MoO2(VI) ions. It is expected that the present compounds may find use in some of the
fields mentioned above.
EXPERIMENTAL
Materials
The estimation of metal, DMF contents, spectral (IR, reflectance, ESR) studies and
the magnetic susceptibility measurements were carried out by the methods described in
Appendix-3.
Synthesis of 19
Polystyrene 3-formylsalicylate (1.0 g) was swollen in DMF (50 mL) for 45 min.
To this suspension, o-hydroxyphenylurea (0.711 g, 4.68 mmol) and ethyl acetate (100 mL)
were added, while stirring magnetically. The mixture was refluxed for 8 h and the solid
product obtained was suction filtered, washed with DMF, ethyl acetate, MeOH and dried
as mentioned elsewhere. Yield = 55%. IR bands (KBr): (C==O)(carbonyl) (1735 cm-1),
(C==O)(ester) (1725 cm-1), (C==N)(azomethine) (1630 cm-1), (CO)(amino moiety)
(1528 cm-1) and (CO)(aldehyde moiety) (1515 cm-1).
Syntheses of 20-24
1.0 g of 19 was allowed to suspend and swell in DMF (100 mL) for 1 h. A DMF
solution of appropriate metal salt/compound (2.34 mmol) was added to the above
suspension. The mixture was refluxed on a water bath for 8-10 h and the products obtained
were suction filtered, washed several times with ethyl acetate and DMF. The products
were then dried as mentioned above. Yield = 55-68%.

Polystyrene-3-formylsalicylate reacts with o-hydroxyphenylurea in DMF in 1:4
molar ratio and forms the polystyrene-anchored Schiff base, PSCH2-LH3 (19) (Scheme 7).
138
The latter reacts with appropriate metal salt/compound and forms the corresponding
polystyrene- anchored coordination compounds (Scheme 8).
H
PS
O
O
C
OH
HO
e
t
a
t
e
c
a
l
y
h
t
e
,
F
M
D
H2 N C
reflux
19
+ H 2O
[Scheme-7]
PSCH2LH3 (19) + Cu(OAc)2H2O DMF
[PSCH2LH2Cu(OAc)(DMF)] (20) + AcOH

reflux
+ H2O
PSCH2LH3 (19) + Cd(OAc)22H2O DMF
[PSCH2LH2Cd(OAc)(DMF)] (21)
reflux
+ AcOH + 2H2O
PSCH2LH3 (19) + Mn(OAc)24H2O DMF
[PSCH2LH2Mn(OAc)(DMF)3] (22)
reflux
+ AcOH + 4H2O
PSCH2LH3 (19) + FeCl3 DMF
[PSCH2LH2FeCl2(DMF)2] (23) + HCl

reflux
PSCH2LH3 (19) + [MoO2(acac)2] DMF
[PSCH2LH2MoO2(acac)] (24) + acacH

reflux
[Scheme-8]
The per cent reaction conversion (PRC) of the compounds lies between 44.8-81.3
(Table 4.1) and the metal binding capacity (MBC) of 19 between 0.32-0.60 mmol of metal
per g of the latter. 19 and its coordination compounds (20-24) are insoluble in water and in
common organic solvents. DMF has been chosen as the solvent due to its high dielectric
constant and more effective in swelling the resin. DMF is lost completely by heating 20,
21, 22 and 23 at 118, 183, 154 and 135 oC respectively in air-oven.
3-Formylsalicylic acid exhibits the (C==O)(carboxylic) stretch[9] at 1660 cm-1.
The appearance of a new band at 1725 cm-1 due to the (C==O)(ester) stretch in
139
polystyrene-3-formylsalicylate is indicative of the covalent bond formation via ester
linkage[337]. The disappearance of the broad feature of the OH group on anchoring with
PSCH2Cl also suggests the covalent bond formation involving OH group of carboxylic
moiety and CH2Cl group of chloromethylated polystyrene moiety[188,338]. The band at
1250 cm-1 in PSCH2Cl due to the (CCl) stretch, disappears in polystyrene-3formylsalicylate, which further supports the covalent bond formation[339]. The resulting
polystyrene-anchored Schiff base (19) (Fig.4.1) shows prominent bands at 1735, 1725,
1630,
1528
and
1515
cm-1
due to
(C==N)(azomethine), (CO)(amino
the (C==O)(carbonyl),
(C==O)(ester),
moiety) and (CO)(aldehyde moiety)
stretches respectively. The band due to the (CO) (aldehyde moiety) undergoes a
positive shift by 10 cm-1 in 20-24 (Fig.4.2) which indicates the involvement of phenolic
O atom of the aldehydic moiety[9] towards coordination. The data rule out the adoption of
the bimetallic structure in 20-24. The (CO)(amino moiety) stretch remains almost
unaltered in 19 and 20-24 indicating the non-involvement of phenolic O atom of amino
moiety towards coordination. The shifting of the (C==N)(azomethine) stretch towards
lower energy by 10-25 cm-1 in 20-24 suggests the participation of azomethine N towards
coordination[9]. The (C==O)(ester) stretch remains at the same energy in 20-24 indicating
the non-participation of the ester O atom(s) on coordination. The (C==O)(carbonyl)
stretch occurring at 1735 cm-1 also remains unaltered in 20-24 ruling out the possible
enolisation and coordination of O atom upon coordination. Although 19 is potentially a
pentadentate ligand, but it acts as a monobasic bidentate ON donor ligand coordinating
through its phenolic O and azomethine N atoms. The presence of the new non-ligand
bands between 521-550 cm-1 and 430-470 cm-1 due to the (MO) and (MN) stretches
support the coordination through O and N atoms of 19 respectively[296]. The as(OAc) and
s(OAc) stretches of free acetate ions occur at 1560 and 1416 cm-1 respectively[148]. The
appearance of the bands in 20-22 between 1587-1595 cm-1 and 1355-1362 cm-1 due to the
as(OAc) and s(OAc) stretches respectively indicates the presence of the coordinated
acetato group in these compounds. The energy separation (225-240 cm-1) between
as(OAc) and s(OAc) stretches is >144 cm-1 which indicates the monodentate nature of
the acetato ligand. DMF shows a band at 1680 cm-1 due to the (C==O) stretch[327]. This
band shifts to lower energy by 12-27 cm-1 in 20-23 and this indicates the involvement of O
140
atom of DMF towards coordination[327]. The presence of bands at 935 and 905 cm-1 due to
the s(O==Mo==O) and as(O==Mo==O) stretches respectively in 24 suggests the
presence of a cis-MoO2 configuration in it[262]. Acetylacetone is coordinated as a
monobasic bidentate OO donor ligand in 24 as evident by the presence of two new bands
one at 1567 cm-1 and other at 1378 cm-1 due to the s(CO) and as(CO) stretches
respectively[316].
The reflectance spectrum of 20 shows a broad band at 18700 cm-1 due to the 2B1g
2A1g, 2B2g and 2Eg transitions for the square-planar arrangement of 19 around Cu(II)
ion[301]. 22 exhibits three bands at 18500, 22870 and 25700 cm-1 due to the 6A1g
4
T1g(G)(1), 6A1g 4T2g(G)(2) and 6A1g 4A1g(G)(3) transitions respectively in an
octahedral environment[300]. 23 shows three bands at 12250, 15800 and 22200 cm-1 due to
the 6A1g ground term to quadrate excited states, viz. 6A1g 4T1g(G)(1), 6A1g 4T2g(G)(2)
and 6A1g 4A1g(G)(3) transitions in octahedral symmetry[300]. It is of interest to note that
although both Mn(II) and Fe(III) have 6A1g ground state, all bands occur at lower energy
in 23 than those in 22. This is due to the lower value of Racah parameter (B and C) in 23
as compared to those of 22[300].
ESR studies
The X-band ESR spectrum of 20 (Fig.4.3) has been recorded in DMSO at 77K
using DPPH as marker. The spectrum shows usual anisotropic pattern with two g values,
which are characteristic of axial symmetry. The spin-Hamiltonian parameters are: A|| =
1.70 10-2 cm-1, A = 3.2 10-3 cm-1, g|| = 2.24, g = 2.08, gav = 2.1, G = 3.15, Pd = 1.76
10-2 cm-1, = 0.48, g||/A|| = 132, 2 = 0.79. The pattern g|| > g > 2 suggests a tetragonal
distortion around Cu(II) ion corresponding to the elongation along four-fold symmetry z
axis with dx2-y2 as the ground state[340]. The value of g|| is less than 2.3 suggesting the
covalent character of 19. The value of G (3.15) is less than 4, which is indicative of strong
field nature of 19 in 20[340]. The value of covalent parameter, 2 (in-plane bonding) is
0.79 which suggests the considerable covalent bonding[341]. The lower value of Pd (1.76
10-2 cm-1) in comparison to the free ion value (3.5 10-2) indicates the presence of
covalent character between metal-ligand bonding. The absence of a band at ~1500 gauss
due to the Ms = 2 transition in the present case precludes the presence of CuCu
141
interaction. This results a magnetically dilute environment around the metal atom as the
pathway for dimer formation is blocked.
The room temperature magnetic susceptibilities and magnetic moments of 20, 22
and 23 are presented in the Table 4.2. The magnetic moment of 20 is 1.87 B.M. which is
in the expected range reported for magnetically dilute Cu(II) compounds[112]. The
magnetic moment of 22 is 5.84 B.M., expected for the high-spin, magnetically dilute
Mn(II) compounds[107]. The magnetic moment of 23 is 5.82 B.M. which is closer to the
spin-only value reported for a majority of octahedral compounds[112]. The coordination
compounds, 21 and 24 are diamagnetic as expected.
CONCLUSION
The polystyrene anchored Schiff base, PSCH2LH3 (19) behaves as a monobasic
bidentate ON donor ligand in magnetically dilute 1:1 coordination compounds (20-24).
The coordination numbers of respective metal in 20, 21, 22, 23 and 24 are 4, 4, 6, 6 and 6
respectively. A square-planar structure to 20, a tetrahedral structure to 21 and the
octahedral structures to 22-24 are proposed. 22 and 23 are paramagnetic, while others are
diamagnetic. A tetragonal distortion around Cu(II) ion in 20 corresponds to the elongation
along four fold symmetry z-axis with dx2-y2 as the ground state.
Fig.1.1 IR spectrum of LH3 (1)
Fig. 1.2 IR spectrum of [FeCl(LH)(MeOH)]2 (4)
Fig. 2.1 IR spectrum of L'H3 (8)
Fig.2.2 IR Spectrum of [Mn(OAc)(L'H2)(MeOH)2] (11)
Fig.2.3 ESR Spectrum of [Cu(OAc)(L'H2)] (9)
Fig. 3.1 IR Spectrum of LH3 (14)
Fig. 3.2 IR Spectrum of [Cu(OAc)(LH2)] (15)
Fig. 3.3 Reflectance Spectrum of [Cu(OAc)(LH2)] (15)
Fig. 4.1 IR Spectrum of PSCH2LH3 (19)
Fig. 4.2 IR Spectrum of [PSCH2LH2Cd(OAc)(DMF)] (21)
Fig. 4.3 ESR Spectrum of PSCH2LH2Cu(OAc) (DMF)] (20)
APPENDIX-1
(ABBREVIATIONS)
142
S.N.
Abbreviation
Full Form
1.
acacH
acetylacetone or pentane-2,4-dione
2.
BCPDZC
bis(cyclopentadienyl)zirconium(IV) chloride or [Cp2ZrCl2]
3.
bipy
2,2'-dipyridyl
4.
bn
butylenediamine or butane-1,4-diamine
5.
ButOH
t-butyl alcohol or 2-methylpropan-2-ol
6.
Cp2
cyclopentadiene or ferrocenyl
7.
CAC
Chloroacetyl Chloride or ClCH2COCl
8.
DMF
dimethylformamide
9.
DMSO
dimethylsulphoxide
10.
en
ethylenediamine
11.
Et
ethyl
12.
EtOH
ethanol
13.
hour(s)
14.
HDAOHTZAc
hexadecaaquaoctahydroxotetrazirconium(IV) acetate or
[Zr4(OH)8(H2O)16](OAc)8
15.
HDAOHTZC
hexadecaaquaoctahydroxotetrazirconium(IV) chloride or
[Zr4(OH)8(H2O)16]Cl8
16.
HDAOHTZITC
hexadecaaquaoctahydroxotetrazirconium(IV) isothiocyanate
or [Zr4(OH)8(H2O)16](NCS)8
17.
MBC
metal binding capacity
18.
Me
methyl
19.
MeOH
methanol
20.
MeONa
Sodium methoxide
21.
oap
2-aminophenol
22.
OEt
ethoxy
23.
OMe
methoxy
24.
ophen
o-phenanthroline or 1,10-phenanthroline
143
25.
OBut
2-methyl-2-propoxide
26.
OPri
2-propoxide
27.
phen
o-phenylenediamine or 1,2-diaminobenzene
28.
pn
propylenediamine or propane-1,3-diamine
29.
PRC
Per cent reaction conversion
30.
PriOH
Propan-2-ol
31.
py
pyridine
32.
sal
salicylaldehyde
33.
TEA
triethylamine or Et3N
34.
TEM
triethoxymethane
35.
THF
tetrahydrofuran
36.
TKACACZ
tetrakis(acetylacetonato)zirconium(IV) or
[Zr(acac)4]
37.
TKPZP
tetrakis(2-propoxo)zirconium(IV)propan-2-olate or
[Zr(OPri)4]PriOH
38.
TKSZ
tetrakis(salicylaldehydo)zirconium(IV) or [Zr(sal)4]
39.
TMS
Tetramethylsilane
APPENDIX-2
(MATERIALS AND SOURCES)
144
S.N.
Material
Source
1.
Ammonium molybdate tetrahydrate
BDH
2.
Barium chloride
Ranbaxy
3.
Benzene
Ranbaxy
4.
Bis(acetylacetonato)dioxomolybdenum(VI)
5.
Cadmium(II) acetate dihydrate
6.
Chloromethylated polystyrene, PSCH2Cl
7.
Chloroacetyl chloride
8.
Cobalt(II) acetate tetrahydrate
BDH
9.
Copper(II) acetate monohydrate
IDPL
10.
Dimethylformamide
Ranbaxy
11.
Dioxane
Ranbaxy
12.
Ethyl acetate
Ranbaxy
13.
EDTA
Nice
14.
Eriochrome black-T
Nice
15.
3-Formylsalicylic acid
16.
Glacial acetic acid
17.
Hexadecaaquaoctahydroxotetrazirconium(IV)
acetate
Published procedure[9]
18.
Hexadecaaquaoctahydroxotetrazirconium(IV)
chloride
BDH
19.
Hydrochloric acid
Nice
20.
8-Hydroxyquinoline
BDH
Sigma Chemical Co (USA)
Ranbaxy
BDH
Ranbaxy
145
21.
Iron(III) chloride (anhydrous)
BDH
22.
Manganese(II) acetate tetrahydrate
Sarabhai
23.
Merceptoacetic acid
Ranbaxy
24.
Methanol
Ranbaxy
25.
Murexide
Ranbaxy
26.
Nickel(II) acetate tetrahydrate
27.
Nitric acid
Nice
28.
N-phenylanthranilic acid
Nice
29.
o-aminophenol
CDH
30.
Petroleum ether (b. p. 40-60 oC)
Ranbaxy
31.
polystyrene 3- formylsalicylate
32.
Potassium dichromate
Ranbaxy
33.
Silver nitrate
Ranbaxy
34.
Starch
Nice
35.
Stannous chloride
Nice
36.
Sodium bicarbonate
Ranbaxy
37.
Sodium thiosulphate
Nice
38.
Salicylaldehyde
Sarabhai
39.
Sulphuric acid
Nice
40.
Sodium hydroxide
41.
Urea
42.
Xylenol orange
43.
Zinc(II) acetate dihydrate
S.Ds Fine Chemicals
Ranbaxy
Nice
Ranbaxy
S.Ds Fine Chemicals
APPENDIX-3
(ANALYSES AND PHYSICAL
MEASUREMENTS)
146
The estimation of metal contents in non-anchored and polystyrene-anchored
coordination compounds were carried out in a slight different way. The organic skeleton
of the former (~ 0.1 g) was decomposed with conc. HNO3. In case of the coordination
compounds of Zr(OH)2(IV) ion, the residue obtained was strongly heated and the metal
contents were estimated gravimetrically as ZrO2. In case of the coordination compounds
of rest of the ions, the residue obtained was then dissolved in minimum amount of conc.
HCl and then diluted with distilled water.
The metal ions from the polystyrene-anchored coordination compounds of, Cd(II),
Mn(II) and MoO2(VI) ions were first leached by slow warming of the given amount (~
0.1 g) of the respective compound with 6N AcOH. In case of the polystyrene-anchored
coordination compounds of Cu(II) and Fe(III) ions, the leaching of the corresponding
ions was carried out by slow warming of the compound (~ 0.1 g) with 4N AcOH and 6N
HCl respectively. The organic skeleton left was filtered off and washed repeatedly with
hot 2N AcOH or 2N HCl and finally with distilled water.
The corresponding metal ions were estimated as follows: The Mn(II), Zn(II) and
Cd(II) contents of the respective coordination compounds were estimated by
complexometric titration method against standardized EDTA solution using eriochrome
black-T as the indicator. The Co(II) (under N2 atmosphere) and Ni(II) contents of the
respective coordination compounds were also estimated by complexometric titration
method against standardized EDTA solution but using xylenol orange and murexide as
the indicators respectively. The Cu(II) contents was estimated iodometrically against a
standard solution of sodium thiosulphate to the starch end point. The Fe(III) ions were
reduced to Fe(II) ions with aqueous SnCl2 and then estimated against standard K2Cr2O7
solution using N-phenylanthranilic acid as an indicator. The molybdenum contents of
respective compound was estimated by decomposing the known amount (~ 0.1 g) of the
respective dioxomolybdenum(VI) compound with a few drops of conc. HNO3 and conc.
H2SO4 and then igniting the residue in an electric Bunsen at 500 oC. MoO3 obtained was
dissolved in 6N NaOH and then molybdenum was estimated as bis(8-hydroxyquinolinato)
dioxomolybdenum(VI). The S and Cl contents of given compound were estimated
gravimetrically as BaSO4 and AgCl respectively[344].
147
The elemental analyses (carbon, hydrogen and nitrogen contents) and spectral (IR,
reflectance and NMR) studies were carried out at the Sophisticated Analytical
Instrumentation Centre, Punjab University, Chandigarh. ESR spectra of the copper(II)
coordination compounds were recorded at Sophisticated Analytical Instrumentation
Centre, Indian Institute of Technology, Bombay at 77 K in DMSO. The measurements on
thermal analyses were carried out on a Perkin Elmer (Pyrin Diamond) TGA/DTA high
temperature 115 instrument with a heating rate of 10-1000 oC/min in N2 atmosphere. The
magnetic susceptibility measurements of the coordination compounds were carried out by
Gouys method. The diamagnetic corrections were computed using Pascals constants
and following a procedure specially designed for polystyrene-anchored coordination
compounds[162,345] .
The molar conductances of the polystyrene non-anchored coordination
compounds were carried out in DMF with the help of a Toshniwal conductivity bridge
(CL01-02A) and a dip type cell calibrated with KCl solutions. The molecular weights of
the above coordination compounds were determined by the Rast method using diphenyl
as the solvent[346]. The quantitative estimation of coordinated MeOH/DMF molecules was
carried out by heating the coordination compounds in an air-oven at the appropriate
temperatures.
APPENDIX-4
(TABLES AT A GLANCE)
Table 1.1 Analytical, colour, molar conductance and molecular weight of compounds
S. N.
Compound
Stoichiometry
Colour
1.
C14H12N2O3
Brown
2.
ZnC15H14N2O4
Yellow
3.
3 (M = Co)
Co 2C32H36N4O10
Yellow
4.
3 (M = Ni)
Ni2C32H36N4O10
Brown
5.
Fe2C30H28N4O8Cl
M
(mho cm2
mol1)
obsd(calcd) %
M
256a
(256)
65.48
(65.63)
4.85
(4.69)
10.78
(10.94)
8.2
343.8
(351.4)
18.76
(18.61)
51.45
(51.22)
4.11
(3.98)
8.11
(7.97)
4.5
758.2
(753.9)
15.46
(15.63)
51.12
(50.94)
4.93
(4.78)
7.30
(7.43)
5.8
762.8
(753.4)
15.73
(15.58)
50.86
(50.97)
4.62
(4.78)
7.58
(7.43)
5.5
743.4
(755)
13.97
(14.83)
47.12
(47.68)
3.34
(3.70)
6.98
(7.41)
7.4
437.9
(443.2)
20.73
(20.58)
43.16
(43.32)
4.69
(4.51)
6.47
(6.32)
Brown
M. wt.
obsd(calcd)
6.
ZrC16H20N2O7
Yellow
Abbreviations: aMass spectral data
148
Table 1.2 IR, reflectance spectral data (cm - 1 ) and magnetic moments of the coordination compounds
(C==N)
(azomethine)
(CO)
(CO)(alcohoic)
S. N.
Compound
max
Mag. moment
(B.M.)
1.
1620
1526
2.
1598
1532
984
3.
3 (M = Co)
1603
1552
978
9210, 13550, 19760
4.3
4.
3 (M = Ni)
1600
1546
964
9720, 16390, 25540
2.5
5.
1605
1561
974
12000, 15650, 19000
5.03
6.
1607
1533
980
Diamagnetic
Diamagnetic
149
Table 1.3 Semiempirical ZINDO/1 computed parameters for compounds

S.
N.
Compound
No.of
electrons
1.
96
No.
of Total
double
orbitals
occupied
levels
48
88
Total
energy
(a.u.)
Core-Core
interaction
(kcal/mol)
Heat
of Selected bond lengths and
formation
bond angles
(kcal/mol)
-171.1635
412093.08
-6670.092
1.32Ao;
C(7)=N(8)
C(9)=O(23) 1.22 Ao; C(9)

1.32Ao;
N(10)
C(5)C(7)
1.42A ; C(4)O(18) 1.32Ao;

C(13)O(21) 1.32Ao;
2.
110
55
102
-198.0338
584505.98
-7938.152
Zn(1)O(4)2.165Ao;O(2)
Zn(1)N(3) 92.508o; N(3)
Zn(1)O(4) 100.303 o.
150
Table 2.1. Analytical, molar conductance and molecular weight of compounds

S. N. Compound
1.
Stoichiometry
C16H13N2O4Cl
M
(mho cm2 mol1)
obsd(calcd) %
M. wt.
obsd(calcd)
Cl
332.5 a
(332.5)
57.44
(57.74)
3.82
(3.91)
8.45
(8.42)
10.43
(10.68)
13.78
(13.99)
47.45
(47.58)
3.12
(3.30)
6.25
(6.17)
7.95
(7.82)
2.
CuC18H15N2O6Cl
8.3
423.4
(454)
3..
10
CdC18H15N2O6Cl
6.3
513.8
(502.9)
22.58
(22.35)
42.72
(42.95)
2.92
(2.98)
5.63
(5.57)
7.17
(7.06)
4.
11
MnC20H23N2O8Cl
5.3
530.2
(509.4)
10.61
(10.78)
47.25
(47.11)
4.62
(4.52)
5.67
(5.50)
6.84
(6.97)
5.
12
FeC17H16N2O5Cl3
7.2
478.6
(490.5)
11.36
(11.42)
40.78
(41.59)
3.19
(3.26)
5.58
(5.71)
21.93
(21.71)
8.3
561.2
(590.5)
16.35
(16.26)
44.52
(44.71)
3.81
(3.90)
4.62
(4.74)
6.14
(6.01)
6.
13
MoC22H23N2O9Cl
151
Table 2.2. IR, reflectance spectral data (cm -1 ) and magnetic moments of the coordination compounds
(CO)
()
(CO)
(MeOH)
S. N.
Compound
1.
1728
1510
1713
1512
1586
1375
17450
1.87
3.
10
1716
1517
1595
1372
Diamagnetic
4.
11
1698
1514
1592
1380
992
16236, 23400, 25570
5.81
5.
12
1714
1512
994
12450, 15000, 19220
5.78
6.
13
1700
1516
974
Diamagnetic
(C==O)
(-lactam)
as(OAc)
s(OAc)
max
Mag.
moment
(B. M.)
152
Table 3.1. Analytical, molar conductance and molecular weight of compounds

S. N.
Compound
Stoichiometry
M
(mho cm2
mol1)
330 a
(330)
2.
3.
4.
5.
6.
14
58.67
(58.18)
7.3
467.4
(451.5)
13.94
(14.06)
15
4.36
(4.24)
8.35
(8.48)
9.57
(9.70)
47.65
(47.84)
3.63
(3.54)
6.31
(6.20)
7.15
(7.09)
4.3
523.6
(510.9)
11.64
(11.53)
46.83
(46.98)
4.56
(4.70)
5.62
(5.48)
6.37
(6.26)
16 (M = Co)
6.8
522.6
(510.7)
11.37
(11.49)
46.87
(46.99)
4.85
(4.70)
5.59
(5.48)
6.41
(6.26)
16 (M = Ni)
16.37
(16.31)
44.67
(44.91)
4.13
(4.08)
4.61
(4.76)
5.57
(5.44)
19.18
(19.35)
40.93
(40.75)
3.28
(3.40)
5.77
(5.94)
6.63
(6.79)
C16H14N2O4S
CuC18H16N2O6S
CoC20H24N2O8S
NiC20 H24N2O8S
obsd (calcd.) %
H
1.
M. wt.
obsd.(calcd.)
17
MoC22H24N2O9S
9.6
565.6
(587.9)
18
ZrC16H16N2O7S
5.3
495.5
(471.2)
153
Table 3.2. IR, reflectance spectral data (cm -1 ) and magnetic moments of the coordination compounds
S. N.
Compound
as(OAc)
s(OAc)
(CO)
(MeOH)
max
1.
14
1710
1528
15
1680
1537
1570
1345
17300
1.82
3.
16 (M = Co)
1676
1535
1572
1352
966
8650, 17340, 19500
4.78
4.
16 (M = Ni)
1680
1536
1564
1340
972
8670, 15860, 24500
3.32
5.
17
1672
1532
970
Diamagnetic
6.
18
1675
1534
Diamagnetic
(C==O)
(thiazolidinone)
(CO)
Mag.
moment
(B.M.)
154
Table 4.1. Analytical, MBC and PRC values of polystyrene-anchored coordination compounds
obsd(calcd)%
S. N.
MBCa
(mmol of metal/g
Compound
M
DMF
PRCb
of the resin)
1.
20
2.9 (4.84)
3.3 (5.56)
0.46
59.9
2.
21
6.4 (8.25)
4.2 (5.36)
0.57
77.5
3.
22
2.5 (3.79)
9.9 (15.10)
0.46
66.0
4.
23
1.8 (4.02)
4.7 (10.50)
0.32
44.8
5.
24
5.8 (7.13)
0.60
81.3
Abbreviations: aMBC = [M% (observed) 10] /(atomic weight of metal); bPRC = [M% (observed) 100] / M% (calculated) on
the basis of 100% reaction conversion of polystyrene-anchored ligand to polystyrene-anchored coordination compounds.
155
Table 4.2. IR, reflectance spectral data (cm - 1 ) and magnetic moments of the coordination compounds
S. N.
Compound
(C==N)(azo
-methine)
(CO)
()
as(OAc)
s(OAc)
(C==O)
(DMF)
max
Mag.
moment
(B. M.)
1.
19
1630
1515
20
1618
1522
1587
1362
1656
18700
1.87
3.
21
1620
1523
1595
1355
1662
Diamagnetic
4.
22
1615
1520
1594
1358
1653
18500, 22870, 25700
5.84
5.
23
1605
1523
1668
12250, 15800, 22200
5.82
6.
24
1615
1518
Diamagnetic
156
APPENDIX-5
(FIGURES AT A GLANCE)
157
OH
HO
OH
HO
O
C
HO
1 (keto-form)
H
CH
HO
Me
O
O
O
Me
O
Me
Me
Zn
Me
O
1 (enol-form)
HO
OH
C
H
[2]
[3; M = Co, Ni]
H
H
l
C
HO
Me
O
e
F
e
F
Me
O
OH
Zr
N
OH
l
C
O
Me
C
OH
HO
[4]
[5]
Me
158
6; Energy optimized structure of 1
7; Energy optimized structure of 2
159
HO
H
C
C
OH
H
C
Cl
O
Cu
HO
Cl
OAc
[8]
[9]
Cl
H
C
HO
C
C
HO H
C
C
Cd
O
Mn
OAc
O
Me
[10]
Me
OAc
H N
Cl
[11]
160
HO
H
Cl
Me
O
Me
O
C
Me
O
O
[13]
H
N
H
O
Cu
C
HO
C
H
[14]
[15]
O
H
C
OH
C
H
Me
O
M
C
OAc
O
Me
[16; M = Co, Ni]
OH
O
H
[12]
OH
Mo
O
Cl
Fe
O
Cl
Me
Cl
HO
OAc
161
Me
Me
OH
O
Zr
Me
OH
N
C
H
Mo
C
HO
OH
HO
C
H
[17]
[18]
H
C O
PS
O
C
H
PS
OAc
Cu
C O C
HO
OH
C O
O
H
NH
N C
DMF
HO
N
H
[19]
[20]
OAc
H
PS
PS
O
C
O
C
DMF
Cd
C O
OAc
DMF
N
C
Mn
H
HO
[21]
DMF
C O
NH
NH
HO
[22]
DMF
162
H
H
PS
C O
Me
H
O
C
DMF
PS
Cl
Cl
DMF
C O
NH
O
O
NH
HO
HO
[23]
[24]
R'
R'
R
R
C
R
Me
Mo
Fe
H
R'''
R''
[26]
H
Ph
C
N
Ph
N
O
M
C
Ph
C
H
N
Ph
[27]
Me
C2H4
N
C
R''
[25]
Me
163
Me
HO
H
C
HO
H
H
[28]
R
C
[29]
HO
PS
C
HO
OH
Fe
CH2
C
CH2
[30]
[31]
Me
Me
C
H2C
Me
H
N
HN
CH2
OH
H
N
HN
CH2
HC
Me
Me
Me
C
OH
H
OH N
HC
Me
CH2
[32]
Me
Me
164
O
R
PSCH 2
OH
OH
N
OH
C
H
OH
Et
Et
OH
C
C
A
O
C
N
OH
Et
Et
[35C]
O
M
Me
Me
A
M
O
[35B]
Et
Me
[35A]
Me
H
C
H
Me
[34]
H
C
[33]
OH
H
H
H2N
NH
C
C
Me
O
COOH
[36]
[37]
165
Me
O
S
C
N
C
O
Cl
OMe
H
C
NH2
O
N
H2N
S
NH
O
N
CH2
Me
COOH
[38]
[39]
O
O
Me
CH2
O
C
N
C
C
O
Cl
HN
C
N
NH2
OMe
MeO
S
OH
[40]
[41]
Ph
R
Ph
Me
N
C
R
HO
N
Ph
[42]
Ph
OH
C
Me
Me
Me
Me
[43]
166
Cl
H2O
Me
N
HO
O
Me
H
OH2
Cl
[44]
[45]
NH
N
N
H
M2+
SH
O
N
H
[46A]
[46B]
OH
Cl
S
N
Me
[47]
NH
Me
167
H
CH2Ph
Ph
C
OH
OH
HS
Ph
Ph
CH2Ph
Ph
[48]
PhCH2S
C
Ph
H
C
Ph
H
O
Ph
O
M
S
HO
C
CH2
NH
C
C
Ph
N
CH2OCOR'
SCH2Ph
COOH
[49]
[50]
CH2OCOR'
O
C
N
R
Cl
C
O
N
H
HX
C
CH2
[51]
R
H
[52]
168
O CH2PS
O CH2PS
O
R
C
OH
C
OH
HO
CH2
C
CH
C
R'
R''
N
R''
[53]
Fe
Fe
OH
HO H 2C
OH
HO
CH
N
CH 2 OH
NH
C
N
N
H2C
[54]
[55]
Me
Me
OH
HO
H
N
Ph
N
H
[56]
H
Me
Me
HC
C
OH
Ph
CH2
C
R'
169
O
C
H2C
HO
N
H2C
H
C
C
H
HO
[57]
OH
Me
Me
O
O
OH
N
C
OH
[58]
[59]
N
C
C
N
OH
N N
H2N
[60]
[61]
170
OMe
N
C
N
Me
C
O
S
N
COONa
H2N
CH2S
ONa
NH
[62]
S
CH2
N
Me
COO
N
N
O
Me
N
O
HN
O
H
NH2
M
C
MeO
Me
N
N
N
C
S
[64]
Me
C
N
H
N
H
C
N
N
ClO4
H
C
S
N
H
[65]
H
N
R'
[63]
R'
Me
171
N
C
N
H
CH2
CH2
CH2
HO
CH2
[66]
[67]
H
Me
H
N
OH
N
N
Me
O
N
Me
CH2 PS
Ph
[68]
[69]
Me
Et
HO
OH
C
C
C
Me
Cl
Cl
O
Fe
X
N
Cl
Fe
O
Cl
H
Et
N
C
Me
Me
[70]
[71]
C
H
172
O
O
Me
CH2
O
N
C
Fe
Cl
O
Me
Me
3 H 2O
HN
Cl
.
Me
Me
N H2
O
S
M eO
S
[72]
[73]
H
N
H
N
Me
OH
( H2C) 2
OH
Me
NH
( H2C)3
( H2C) 2
OH
Me
OH
Me
[74]
[75]
N
CH2 N
N
Me
COO
S
N
OH2
Fe
H
N
O
MeO
OH2
[76]
Cl
R
Cl2
Fe
NH2
S
[77]
173
OH
HO
R
N
C
H
CH2
CH2
N
CH2
R
N
CH2
CH2
C
H
CH2
[78]
C
OH
OH
OH
HO
CH2
CH2
C
H
[79]
Me
H
OH
CMe3
OH
OH
C
Me
OMe
[80]
[81]
CMe3
174
Ph
Ph
H N
OMe
HO
C O Y
Ph
H2O
O H2
Y O C
Ph
N
Ph
H
CH2NHpy
Ph
[82]
[83]
HO
Me
N H2
Cl
N
O
R
Cl
H
C
R'
NH2
H 2N
Me
OH
[84]
[85]
NH2
OH
HO
C
C
H
Me
HO
O
R
N
S
O
[86]
[87]
R
N
C
H
175
O
H
R
C
R
O
O
Cl
R
C
Me
Me
[88]
C
C
Me
NH
COONa
[89]
Cl
O
NH
N
O
C
N
O
H
NH
Me
Me
Me
Cl
Me
Me
S
C
C
O
N
NH
H2O
O
OH2
Me
H2O
Me
C
O
OH2
Cl
[90]
[91]
Ph
H
N
O 2N
Me
H2O
Me
Cl
Ph
C
R
NO 2
O 2N
NO 2
[92]
OH
C
R
OH
A
[93]
176
HO
R
N
N
OM e
SO3 Na
SO3H
OH HO
OH HO
R
SO3H
SO3 Na
[94]
[95]
H
N
N
R'
HO
C
Me
H C H
N
C
C
Me
R'''
H
R''
HO
[96]
[97]
Me
C
Me
H
HOOC
[98]
177
Cl
Cl
H2
N
NH
H2
N
NH
M
H2O
Cl
Cl
M
H2O
Cl
C
Me
Cl
Me
[99]
HN
S
C
NH
H
N
C
C
Me
NOH
OMe
[100]
H
C
H
C
N
H
[101]
C
H
O
178
N
M
[102]
[103]
HO
OH
O
O
Me
OH
S
N
H
[104]
N
H
[105]
O
C
Me
OH
OH
R
A
CH
CH2
R'
CH2
Me
C
N
Et
Et
R'
[106]
[107]
CH
Me
N
C
C
N
Me
179
H
C
C
N
C
S
CH2
HS
SH
CH2
[108]
H
C
N
N
C
CH2
S
C
CH2
N
N
C
[109]
R
Et
R
N
N
OH
C
H
R
R
[110]
[111]
180
Ph
HOOC
C
C
M
C
Me
C
Me
R'
[112]
Ph
Me
OH
OH
C
HOH2C
Me
H2C
CH2
[113]
[114]
Me
N
HO
N
C
[115]
OH
C
N
[116]
Me
181
Me
Me
C
S
O
H
H C
H2
C
O
NH
M
C
x H2 O
NH
C
H2
S
C
C
Me
Me
[117]
[118]
H
N
C N
OH
R''
R'''
HO
R'
[119]
[120]
R
C
C
N
R
C
N
C
[121]
C
H
SH HS
C
H
182
R'
N
C
N
R'
C
SH
N
CH2
SH
NH
CH2
CH2
[122]
CH2
CH2
C
H
CH2
[123]
Cl
O
NH
N
R'
R
C
Me
Me
Me
Cl
C
Cu
H2O
R''
OH2
[124]
[125]
Cl
O
NH
Me
O
Me
C
O
O
Me
C
C
Me
O
N
Me
Cu
C
Me
R'
O
N
NH
HS
R''
Cl
[126]
[127]
183
OH2
O
N
M
H
H
CH2
[128]
[129]
R
C
H
OH
OH
C
C
R''
R'
R''
R''
R'
[130]
[131]
Ph
H
Ph
O
Ph
Y
Y
N
Cu
Cu
N
Ph
Ph
O
C
H
R'
Ph
[132]
[133]
184
H
C
C
Cl
O
Cu
Cu
. 3 H2O
Cu
N
Cl
[134]
O
C
N
N
C
Me
N
C
H2
H2
C
C
N
H2
C
Me
N
C
Me
[136]
OH
C
H
MeO
C
H
[137]
C
Me
C
N
[135]
MeO
N
R
[138]
185
O
H
C
N
C
N
H
H
N
C
N
C
S
HO
H
N
C
SH
HO
[139]
Me
H
O
O
Zn
Zn
N
Me
O
Me
Me
H
C
[141]
H
N
N
N
C
H
[142]
C
N
[140]
186
XH
N
XH
N
H2
N
Cp
Cp
Py/morpholine
CH2
H
Zr
Zr
CH2
Cp
Cp
N
H2
OH
Py/morpholine
OH
Cl2
Cl2
[143]
R'
[144]
R'
R
R''
R''
OH
[145]
[146]
Me
C
HO
OH
C
H
Fe
O
CH2PS
Me
[147]
O
C
[148]
187
X
C
OH
HO
Fe
[149]
[150]
R''
R'
HX
N
C
OH HX
N
R
N
C
C
C
R''
Me
[152]
N
Cp
XH
Cl
CH2
R'
[151]
Cp
(CH2) n
Zr
Cl, C6H6
Reflux, NaOH, -NaCl
CH2
Zr
CH2
Cp
XH
[153]
Cl2
Cp
[154]
Cl2
SR
188
HO
OH
HO
OH
CH2 PS
[155]
[156]
OH
R''
OH HO
R
C
R''
C
R'
R'
[157]
R
R'
R'
C
N
H
O
C
Ph
Zr
Zr
Ph
O
H
OH2
H2O
OH
HO
OH
HO
H2O
Zr
Ph
C
Zr
O
H
C
N
N
O
Ph
S
HO
Zr
O
R'
R'
H
O
N
C
OH2
H
O
Me
[158]
OH
O
R
C
H
Zr
O
H
Me
O
[159]
189
Cl
OH
HO
N
H
C
Zr
OH
O
Cl
[160]
[161]
R
C
XH
HX
C
CH
HC
C
R
N
R
C
R
[162]
R'
OH
C
N
N
HO
C
H
HO
HO
Fe
H
H
C
N
OH
HO
[163]
C
H
R'
[164]
190
Fe
Fe
R
R
C
H
C
C
C
R'
R'
OH
HO
C
R'
R'
[165]
R
Me
H
C
N
C
C
Zr
C
Cl
Me
Me
Cl
Me
C
C
C
O
Cl
C
H
N
N
O
[167]
Me
CMe3
HO
N
N
C
H
[168]
Me
C
H
N
N
C
H
Me Me
Cl
Me
CMe3 Me3C
OH
Zr
[166]
Me3C
N
Cl
Cl
Me
Zr
O
Zr
H
C
Me
Cl
Me
Cl
C
Me
[169]
O
H
C
Me
191
O
Me
C
H2C
S
Me
C
Mo
O
H
N
C
O
H
C N
O
H
Me
Me
[171]
OH S
C
N
H
[172]
O
Mo
Mo
N
[173]
O
acac
[170]
C
N
Me O
192
O
O
173
2nA
O
Mo
2n
N
X
A
[174]
O
HO
C
HN
Me
OH
R'
C
R
NH
[175]
[176]
O
PS
O C
PS
OH
OH
HO
O
C
NH
NH2
[177]
NH2
193
N
H23C11
Mo
Mo
NH2
HO
O
O
HO
[178]
[179]
OH
OH
S
R
C
R
N
[180]
H
C
H
N
(CH2)n
OH
OH
OH
HO
[181]
H
N
C
N
O
(C H 2 ) n
Mo
R
O
C
N
Mo
py
R
O
py
[182]
Me
NOH HON
Me
Me
Me
N
R
[183]
194
PSCH2O
C
H
OH
HO
OH HO
C
CH2
CH2
[184]
[185]
O
O
Me
O O
C
Mo
Mo
C
Me
Me
C
N
O O
Me
O
R
[186]
NH2
H2N
X'
N
C
S
Cd
X'
N
N
X X
N
N
Cd
NH2
H2N
[187]
H
C
X'
X'
195
H
S
C
H
SH
Me
Me
[188]
Me
O
Me
O
N
O
OH2
N
H
H
C
OH2
M
N
O
S
[189]
OH
OH
OH
HO
C
N
[191]
Me
[190]
N
HS
OH
HO
[192]
196
NO2
O2N
OH HO
H
N
C
Me
H
Me
N
Me
[194]
C
R'
SH
HS
OH
OH
C
N
N
H
H
N
Me
Ph
[193]
R'
Ph
N
H
[195]
[196]
N
C
[197]
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SUMMARY
216
Salicylaldehyde reacts with o-hydroxyphenylurea in equimolar ratio in MeOH and
forms the Schiff base, LH3. The latter reacts with Zn(II), Co(II), Ni(II), Fe(III) and
Zr(OH)2(IV) ions in equimolar ratio in MeOH and forms the coordination compounds of
the types, [Zn(LH)(MeOH)], [M(LH)(MeOH)2]2 (M = Co, Ni), [FeCl(LH)(MeOH)]2 and
[Zr(OH)2(LH)(MeOH)2]
respectively.
The
coordination
compounds
have
been
characterized on the basis of elemental analyses, molecular weight, spectral (IR,

reflectance and
H NMR) studies, thermo-gravimetric analyses and the magnetic
susceptibility measurements. The coordination compounds are insoluble in H2O, MeOH

and EtOH but are soluble in DMF and DMSO. Their experimental molar conductance (M
= 4.58.2 mho cm2 mol-1 in 10-3 M DMF solution) show that they are non-electrolytes.
[Zn(LH)(MeOH)] and [Zr(OH)2(LH)(MeOH)2] are monomeric, while [M(LH)(MeOH)2]2
(M = Co, Ni) and [FeCl(LH)(MeOH)]2 are dimeric in nature. LH3 behaves as a dibasic
tridentate ONO donor ligand. [M(LH)(MeOH)2]2 (M = Co, Ni) and [FeCl(LH)(MeOH)]2
are
paramagnetic
and
possess
octahedral
geometry.
[Zn(LH)(MeOH)]
and
[Zr(OH)2(LH)(MeOH)2] are diamagnetic and possess tetrahedral and pentagonal

bipyramidal geometries respectively.
The above Schiff base LH3, undergoes cyclo-condensation with CAC in the
presence of Et3N and forms the corresponding azetidin-2-one, L'H3. The latter reacts with
Cu(II), Cd(II), Mn(II), Fe(III) and MoO2(VI) ions in 1:1 molar ratio in MeOH and forms
the corresponding monomeric coordination compounds of the types, [Cu(OAc)(L'H2)],
[Cd(OAc)(L'H2)],
[Mn(OAc)(L'H2)(MeOH)2],
[FeCl2(L'H2)(MeOH)]
and
[MoO2(acac)(L'H2)(MeOH)]. The compounds have been characterized on the basis of

elemental analyses, molar conductance, molecular weight, spectral (IR, reflactance, ESR)
studies and magnetic susceptibility measurements. The experimental molar conductance
data (M = 5.3-8.3 mho cm2 mol-1 in 10-3 M DMF) of the coordination compounds support
their non-electrolytic nature. L'H3 acts as a monobasic tridentate ONO donor ligand. The
coordination numbers of the respective metal are 4, 4 and 6 in the paramagnetic
compounds, [Cu(OAc)(L'H2)], [Mn(OAc)(L'H2)(MeOH)2] and [FeCl2(L'H2)(MeOH)],
while
and
in
diamagnetic
[MoO2(acac)(L'H2)(MeOH)] respectively.
compounds,
[Cd(OAc)(L'H2)]
and
217
The above Schiff base also undergoes cyclo-condensation with mercaptoacetic acid
(HSCH2COOH) in dry C6H6 and forms the corresponding thiazolidin-4-one, L'H3. The
latter reacts with Cu(II), Co(II), Ni(II), MoO2(VI) and Zr(OH)2(IV) ions in 1:1 molar ratio
in MeOH and produces [Cu(OAc)(L'H2)], [M(OAc)(L'H2)(MeOH)2] (here M = Co, Ni),
[MoO2(acac)(L'H2)(MeOH)] and [Zr(OH)3(L'H2)] respectively. L'H3 behaves as a
monobasic tridentate ONO donor ligand. [Cu(OAc)(L'H2)] is paramagnetic and possess
the square-planar geometry. [M(OAc)(L'H2)(MeOH)2] (M = Co, Ni) is paramagnetic with
octahedral geometry. [Zr(OH)3(L'H2)] is diamagnetic with an octahedral geometry.
[MoO2(acac)(L'H2)(MeOH)] is also diamagnetic but with an eight-coordinate structure.
The reaction between polystyrene 3-formylsalicylate and o-hydroxyphenylurea in
DMF
in
the
presence
of
ethyl
acetate
results
in
the
formation
of
polyst yr ene-anchored Schiff base, PSCH 2 LH 3 . A DMF swollen suspension of

the latter reacts with Cu(II), Cd(II), Mn(II), Fe(III) and MoO2(VI) ions in 1:1 molar ratio
and forms the corresponding polystyrene-anchored coordination compounds of the types,
[PSCH 2 LH 2 Cu(OAc)(DMF)],
LH 2 Mn( OAc)(DMF) 3 ],
[PSCH 2 LH 2 Cd( OAc)(DMF)],
[PSCH 2 LH 2 FeCl 2 (DMF) 2 ]
and
[PSCH 2
[PSCH 2
LH 2 MoO 2 (acac)] respect ively. The compounds have been characterized on the basis
of elemental analyses, spectral (IR, reflectance and ESR) studies and magnetic
susceptibility measurements. The per cent reaction conversion of the compounds lies
between 44.8-81.3 and the metal binding capacity of the ligand between 0.32-0.60 mmol
of metal g-1 of the resin. PSCH2LH3 acts as a mo no basic bid ent at e ON do nor
ligand coordinating through phenolic O and azomethine N atoms. The acetato group acts
as a monodentate ligand. Acetylacetone is coordinated as a monobasic bidentate OO donor
ligand. The compounds of Cu(II), Mn(II) and Fe(III) ions are paramagnetic and
magnetically dilute. A square-planar structure for [PSCH 2 LH 2 Cu(OAc)(DMF)], a
tetrahedral structure for [PSCH 2 LH 2 Cd(OAc)(DMF)], the octahedral structures
[PSCH 2 LH 2 Mn(OAc)(DMF) 3 ], [PSCH 2 LH 2 FeCl 2 (DMF) 2 ] and [PSCH 2
LH 2 MoO 2 (acac)] have been suggested.
FUTURE
SCOPE
218
Azetidin-2-ones, the important derivatives of the Schiff bases, have found

extensive uses in biological activities like analgesic, antibacterial, insecticidal,
antimicrobial, anti-inflammatory, anticonvulsant, sedatives, antidepressant, antifungal,
antitubercular, antitumor, cholestrol absorption inhibition and enzyme inhibition
activities[347-366].
Similarly, thiazolidin-4-ones, the another important derivatives of the Schiff bases,
have also played an important role in Medicinal Chemistry[367-369]. They are known to
exhibit
antimicrobial[370],
anticonvulsant[377-379],
vascular[383],
antifungal[371],
nematicidal[380],
anticancer[384],
antibacterial[372,373],
hypoglycemic[381],
septicidal[385],
antitubercular[374-376],
antipsycotic[382],
antithyroid[386],
cardio-
amoebicidal[387]
and
antioxidant[388] activities.
The newly synthesized Schiff bases, their derivatives and their coordination
compounds would be subjected towards some of the above mentioned activities. Further, a
comparative account would be tailored amongst them.
LIST OF PUBLISHED
PAPERS AND THEIR
REPRINTS
List of Papers Published/Accepted in Journals

1. Ligational behaviour of the azetidinone towards some di-, tri-, tetra- and
hexavalent metal ions.
D. Kumar, A. Syamal, V. Pandey and Mukesh Rani, Asian J. Chem., 23, 3517
(2011).
2. Studies on polystyrene-anchored coordination compounds of divalent, trivalent,
tetravalent and hexavalent metal ions with the Schiff base obtained from the
condensation of 3-formylsalicylic acid and o-hydroxyphenylurea.
D. Kumar, A. Syamal, V. Pandey and Mukesh Rani, Asian J. Chem., 23,
5004(2011).
3. Studies on the coordination compounds of thiazolidin-4-one derived from
salicylaldehyde and o-hydroxyphenylurea, D. Kumar, V. Pandey and Anju Gupta,
International J. Chem. Sci., (accepted).
4. Coordination compounds of Schiff base containing urea moiety,

D. Kumar, Arun Syamal, A. Gupta, V. Pandey and Mukesh Rani, J. Indian Chem.
Soc., (under revision).

Ms Vandana Pandey PHD Thesis

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Ms Vandana Pandey PHD Thesis

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STUDIES ON THE METAL COMPLEXES OF FIRST

AND SECOND TRANSITION SERIES

FOR THE AWARD OF DEGREE OF

Dr. DINESH KUMAR

Coordination compounds of Schiff base containing urea

Ligational behavior of the azetidin-2-one derived from

Physico-chemical studies on the coordination compounds of

Materials and sources

Analyses and physical measurements

List of published papers and their reprints

[Zn(LH)(MeOH)] (2), [M(LH)(MeOH)2]2 (3, M = Co, Ni), [FeCl(LH)(MeOH)]2 (4) and

(17) and [Zr(OH)3(L'H2)] (18). The

pent ane-2,4-d io ne)

respect ively. The

polystyrene-anchored coordination compounds (20-24) have been characterized on the

Coordination compounds of manganese(II)

With monodentate ligands:

With bidentate ligands:

cm2 mol-1), four-coordinate compound, [Mn(OAc)L(H2O)] (where LH = 25; R = 3-OMe,

With tridentate ligands:

compound, [PSLMn(DMF)3] (here PSLH2 = 31) is obtained[7] by refluxing a DMF

[PSCH2LMn(DMF)3] (where PSCH2LH2 = 33; R = 3-PSCH2OCO, X = O) has been

have synthesized a dark-brown, polystyrene-anchored six-

coordinate compound, [PSCH2LHMn(DMF)3] (where PSCH2LH3 = 34) by refluxing a

[MnL(LH)](OAc) and [Mn(L''H)2](SCN)2MeOH respectively. A broad band at 22936,

[MnL2]H2OEtOH, [MnL'2]3H2O, [MnL''2]3H2O,

crystallizes in a monoclinic fashion with a = 15.164 , b = 18.793 , c = 11.896 ; =

With tetradentate ligands:

synthesized a four-coordinate, 1:1 electrolyte,

With pentadentate ligands:

With hexadentate ligands:

1:1 electrolyte, [MnClL](ClO4) [here L = 66; R = 2-C5H4N]. L acts as a neutral

With bidentate ligands:

With tridentate ligands:

[PSLFeCl(DMF)2] (where PSLH2 = 31) is obtained by refluxing a DMF swollen

around the metal ion.

have synthesized a reddish-brown, polystyrene-anchored, six-

coordinate compound, [PSCH2LHFeCl(DMF)2] (where PSCH2LH3 = 34) by refluxing a

around the metal ion.

A1 4T2(G) and 6A1 4A1, 4E(G) transitions respectively. Its magnetic

LH coordinates through carbonyl O

With tetradentate ligands:

anchored coordination compound, [PSCH2LFeCl(DMF)] by refluxing a DMF swollen

With pentadentate ligands:

pentadentate ligands. A six-coordinate compound, [FeCl(LH)]2H2O (where Na2LH = 62)

S. sonnei. An octahedral structure (77) has been assigned to it.

With hexadentate ligands:

With bidentate ligands:

It decomposes at 270 oC. It is soluble in DMF and DMSO. LH acts as a monobasic

B1g transition support its square-

[CoCl(LH)(H2O)3] and [Co(LH)2(H2O)2] respectively are obtained. They are insoluble in

They show antibacterial activities against E. coli, K. pneumoniae, P.

aeruginosa, S. typhi, S. dysentriae, B. cereus, C. diphtheriae, S. pyogenes and S. aureous.

With tridentate ligands:

compound, [PSLCo(DMF)3] (where PSLH2 = 31) is obtained by refluxing a DMF

T1g(P)(3) spin-allowed transitions respectively suggest an octahedral environment around

the metal ion.