Chapter-I

1.1 Introduction :

The application of co-ordination compounds in chemistry and technology are

many and varied. The importance of co-ordination compounds is well established.
Naturally occurring co-ordination compounds are vital to living organism. Co-
[1]
ordination chemistry emerged from the work of Alfred Werner, a Swiss chemist
who examined and studied different compounds.

Metal complexes play a variety of important roles in biological systems. Many

enzymes, naturally occurring catalyst that regulate biological processes [2]. There are a
number of ways in which co-ordination compounds are used in the analysis of various
substances.[3-4] The extensive kinetic study of reactions of metal complexes and
application of several spectroscopic methods to establish their structures have further
fine tuned the understanding of it’s class of compound[5].Though several co-ordination
compounds were prepared and their properties studied in the past century, very little
was understood about their structure and bonding in them[6].

In 1893 Werner proposed a theory on these compounds, which gave clear

understanding of the bonding in such compounds. The development of quantum
mechanical understanding of chemical bonds subsequently resulted in clear
[7]
knowledge about the structure and bonding in co-ordination compounds . The
Werner's theory postulated that in co-ordination compounds ,the metal exhibits two
types of valancies primary and secondary[8].The primary valancy is ionisable and
non-directional where as secondary valancy is non-ionisable and directional. The
bond between the ligand and metal ion is due to secondary valancies of metal ion [9].
Soon after the development of electronic theory of valancy : Lewis Kossel, Langmur,
Sidwik[10] ,and others cleared the ideas of primary(oxidation state) and secondary
(coordination number)valancies in complexes.

According to Werners theory ligand donate electron pair to metal ion or atom to
form co-ordinate linkage. This approach was first applied to co-ordination compounds
[11]
by Linus Pauling and Slater (1931) . In 1931 Pauling gave Valence bond theory
which is based on revolutionary idea of hybridization of atomic orbitals[12]. According
to this theory ,the central metal atoms make available equal number of empty orbitals
to it’s coordination number. These orbitals undergo particular type of hybridization
such as sp, sp2, sp3, dsp2 d2sp3, d3sp3 which assigns different shapes to the resulting

1
 Chapter-I

molecules such as linear, trigonal, tetrahedral, square planner, octahedral, pentagonal

and bipyramidal respectively. The filled ligand orbital’s overlap with hybrid orbital’s
of metal ion and forms coordinate bond. This theory explains mainly electronic
structure of central metal ion, shapes of complexes, magnetic moments and
stereochemistry; however, it does not give proper explanation of maximum pairing,
the spectra of the complexes and quantitative interpretation of magnetic properties.

Crystal field theory developed by Bethe[13] and Van Vleck[14] is another approach
to study the complexes .According to this theory, the bond between metal and ligand
is neither due to sharing of electron nor due to interaction of atomic orbitals. Crystal
field theory involves electrostatic approach to the bonding in complexes. It was first
applied to ionic type crystalline substances .This theory considers the metal ion as
being placed in an electrostatic field created by the surrounding molecules or ions.
The electric field due to the ligands lifts the degeneracy of five d-orbitals of central
metal ion and split them into two energy sublevels depending upon the type of
geometry and the nature of ligand, the energy difference between t2g and eg level is
known as crystal field stabilization energy and is denoted by 10 Dq.The magnitude of
10 Dq depends upon the nature of ligands and charge on the central metal ion. It
interprets the magnetic and spectral properties of metal complexes. In its simplest
form, the crystal field theory does not consider the overlapping between the metal and
ligand orbitals. Application of the molecular orbital theory (MOT) to metal complexes
has been developed by Van Vleck. This theory can provide quantitative interpretation
for all the properties of coordination complexes. The bonding between metal ion and
ligand is considered as purely ionic, purely covalent and intermediate.

Rossoti –Rossoti[15] has defined the coordination complex is a species formed

by association of two or more species, each is simple and capable of independent
existence. The common donor atoms present in ligands are N, O and S. If the ligand is
attached to a central metal ion by two or more donor atoms forming heterocyclic ring
[16]
structure is called as chelate , the so formed chelate have exceptionally high
stability. The stability of chelate depends upon the size and number of rings formed
during chelation .Generally coordination compounds formed of a saturated five
membered ring is more stable than those formed of an unsaturated five membered
ring .However, a greater stability is achieved with the formation of six membered ring
.The coordination number of metal is generally 4 or 6. The formation of covalent

2
 Chapter-I

bond with metal ion and donor group may proceed with or without replacement of
hydrogen atom from organic functional groups, which combine with metal ion by
replacement of hydrogen atom from an organic functional group.

1.2 Schiff bases and their metal complexes:

Schiff bases are condensation products of amines with active carbonyl

compounds. They were discovered by a German chemist, Nobel prize winner ,Hugo
Schiff in 1864[17]. The Schiff bases are also called imines, anils and azomethines[18]
They contain azomethine (>C=N) group and hence can act as effective ligand. The
chemistry of the carbon–nitrogen double bond plays a vital role in the progress of
chemical science. Solvent based synthesis of Schiff bases through classical
condensation of aldehyde and amines require PH control, however, the yield of
product, in high and in low PH range (3-4) depending upon the basicity of amines.

' H R'
R
O + N R" N R" + OH 2
R H R

Active carbonyl comp Primary amine Schiff base

(R, R’ and R’’ may be acyclic, alicyclic, aromatic and heterocyclic etc.)

Schiff bases have active imine >(C=N) linkage which provide binding site for
the metal ions through nonbonding electrons of nitrogen .They have also many other
heteroelements like oxygen and sulphur which provide binding sites through
nonbonding electrons .Specially, d block transition metals having vacant d-orbital’s
are able to bind with such ligands. Metal complexes of Schiff bases can be
synthesized by several methods [19], However they are mostly prepared by the addition
of alcoholic or aqueous metal ion solution to the alcoholic Schiff base solution in
presence of sodium acetate or alcoholic or aqueous ammonia. The addition may also
be carried out in neutral medium.
[20, 21]
Schiff Pfeiffer and coworkers[20] extensively used unique method in
which metal complexes of carbonyl derivatives were treated with an alcoholic
solution of amine to obtain the metal chelates of desired Schiff bases, alternatively,
the metal complex of amine was treated with carbonyl compound. This method is
very useful particularly to synthesize metal chelates of unstable Schiff bases .One of
the salient features in the preparation of metal complexes of Schiff bases is PH of

3
 Chapter-I

reaction medium. It plays a significant role in determining the ultimate composition,

constitution, geometry and the structure of resulting complex.

Metal based Schiff base have important applications in medicinal chemistry.

Medicinal science demands such and such type of drug which is more potent,
biologically active, and easily absorbable, with no toxicity and show fast action for
the treatment of diseases.

1.3 Application of Schiff bases in various fields :

Application of Schiff base compounds in various fascinating area is current

research interest to the inorganic chemist all over the world. The continued interest
and quest in designing new Schiff base ligands and their use as a models for protein
metal binding sites in a substantial array of metalloproteinase in biological systems, as
synthetic ionospheres, as a model to study the magnetic exchange phenomena, as
therapeutic agents in chelation therapy for the treatment of metal ion toxication, as
cyclic antibiotics that owe their antibiotic actions to specific metal complexation, to
study the guest host interactions and in catalysis. Recognition of the importance of
complexes containing Schiff base ligands had led to inexpensive synthetic routes for
[22-25]
these compounds Efforts are being invested in developing reliable Schiff bases
and their complexes with transition and non-transition metal ions which have
medicinal, physiological and pharmaceutical application ,also well known as
antibacterial, antifungal, anticancer agents[26-32]. Now a days, the research field
dealing with Schiff base co-ordination chemistry has expanded enormously.

The importance of Schiff base complexes for, bioinorganic chemistry,

biomedical application, supramolecular chemistry, catalysis, medical sciences,
separation encapsulation processes and formation of compounds with unusual
[33]
properties and structures has been well recognized and reviewed . Among the
several classes of ligands, a new tetradentate Schiff base ligands derived from
orthophenylenediamine, salicylaldehyde and isatin /aceyl acetone/2-hydroxy
napthalaldehyde containing oxygen and nitrogen donor sites have been recognized
and synthesized[34] .The different types of Schiff base ligands and their applications
have importance in generating new areas of fundamental chemistry and many
opportunities of applied chemistry. The majority of Schiff base ligands represent
creative and focused efforts to design molecules which will have particular uses.

4
 Chapter-I

The transition metal complexes find extensive applications in technology,

industry and medicine. [35] Some β-diketones complexes have been shown to be good
substitutes for tetraethyllead, the antiknock additive for gasoline. Togther with
triethylalluminium, some lanthanide complexes are used as Ziegler-Natta catalyst for
4-stereospecific polymerization of butadiene.[36] Some carboxylate complexes of
transition metals were used as antioxidant in the chelation therapy to remove 144 Ce -
contamination in the body.[37] The majority of macrocycles represent creative and
focused efforts to design molecules which will have particular uses. It has also been
found that the toxicity decreases with chelation hence the transition metal complexes
derived from ligands capable of forming chelates are of great importance. Many
macrocyclic Schiff base complexes find extensive applications in technology, industry
and medicine.

Schiff bases of thiazoles and benzothiazoles.[38] Possess effective antifungal

activity. Presence of methoxy, halogen and napthyl groups enhance fungicidal activity
towards curvularia. Pyradione Schiff bases showed physiological activity against
[39]
A.niger. Some Schiff bases have quinazolinones show antifungal activity against
candida albicans, trichophytonrebrum, a. niger and microsporumgypseum. Schiff
bases and their metal complexes formed between furan or furyglycoxal with various
amines have shown antifungal activity against helminthosporiumgramineum,
syncephalostr-umracemasus and c. capsici. Transition metal complexes with C, N-
bonded organic ligands have great attention in past years, many of these complexes
are palladium (II) compounds which are found to be very useful in liquid crystal,
catalysis, and in organic synthesis. Recently the term carbopalladium have been
coined although platinum complexes have been less substituted than their palladium
(II) counterparts, their applications are nevertheless important, for example, as
compounds with antitumor activity. Also, photophysical and photochemical properties
of square planer platinum (II) complexes have been described [40] and more recently
cyclometallated platinum (II) complexes have been prepared.

1.3.1 In medical field :

Schiff bases of nitroguanidine with various aldehyde and ketones were studied
for their antineoplastic and tuberculostatic activities. Many other metal chelates were
studied for antitumour and antineoplastic activities. 2-pyridine carbaaldehyde (2-
pyca) and it’s hydrazones are used to collect semen antipode for cyanide poisoning.

5
 Chapter-I

The complexes of Schiff bases derived from 2-pyca and amino acids are powerful
chelates for antibacterial activities. Schiff bases of dehydroacetic acid with benzoyl
hydrazone, salicylic aldehyde and thiosemicar-bazone and their metal chelates have
been studied for applications in biochemically relevant aspects, chemotherapy and
also in the field of agriculture. The imino derivatives of 2-pyca can be used as
chemotherapeutic drugs. Platinum compounds such as cisplatin (cis-[Pt (NH3) 2Cl2]),
carboplatin, nedaplatin, lobaplatin and oxaliplatin are among the most widely used
cancer therapeutic agents. [41] Pt (II) forms complexes with estrogen hormones and is
used as anticancer agent for the treatment of hormone dependant cancer like breast
cancer. [42]

Cobalt complexes of Schiff bases derived from salicyldehyde and diamines

have been proposed as models of Vitamin B12 compounds for similar
physicochemical behaviour such as ability to form stable organometallic compounds
and also models of naturally occurring oxygen carrier capacity to take up oxygen
reversibly. Cobalt complexes of Schiff bases derived from salicylaldehyde and
diamines have proved to be useful in food packages. They have excellent light
resistance property and storage ability and hence prevent degradation of food in
presence of acidic gases like carbon dioxide.

Interest in Schiff base complexes of tin (IV) and organotin (II) moieties have
been shown because of their potential fungicidal and bactericidal activity.[43]It has
been observed that reagents of selective interaction with particular metal ion are very
less. Schiff base complexes of thiosemicarbazide and thiosemicarbazones have been
paid much attention due to their antitubercular activity. Metal chelates are found to
inhibit the tumour growth and such types of metal chelates are used in the treatment
of cancer.[44-45]

1.3.2 In industrial field:

The Schiff base metal complexes carrying molecular oxygen are useful in
biological and industrial processes. The industrial chemists are interested in
developing the homogeneous analogues to metal catalysed oxidation reaction where
as the biochemists are interested in biological oxygen transport.

The schiff bases containing oxygen, nitrogen and sulphur as donor atoms
extend more contribution. Schiff base with sulphur as a donor atoms have been found

6
 Chapter-I

to be more selective as analytical reagents due to it’s large size and less
electronegetivity. They form stable and intense coloured chelates with central metal
[46]
ions. Hence they are successfully used in dyes and pigment industries. The
transition metal complexes are useful for mass dyeing of linear polysters,
polyethylene terephthallet fibers.[47]

1.3.3 In analytical field :

Schiff base and their metal complexes have variety of applications in

analytical chemistry, such as in chromatographic, solvent extraction, separation
techniques, qualitative and quantitative analysis.

Mono and diamines Schiff bases were used in developing qualitative tests for
Cu (II), Ni (II), Co (II), Fe (II), Fe (III), Cd (III), Zn (II), Mg (II) and Pb (II). Schiff
bases with ruthenium, rhodium and iridium complexes have been used as therapeutic
agents and a number of kinetically inert ruthenium (II), rhodium and iridium
complexes have been reported as inhibitors of protein kinases.[48] In chromatography,
polymeric metal complexes of Schiff bases from diamine, bissalicyaldehyde are used
as supports and adsorbents and as covalent bond type polymers, the HPLC resolution
of Cu, Ni, Pd chelates of tetradentate β-ketoimine were carried out. The efficiency of
polymeric schiff base complexes for gas separation was studied by many workers.[49]

1.3.4 As a catalyst :

The past few decades, have witnessed a great deal of interest in chemistry of
transition metal Schiff base chelates because of their importance as catalysts in
reactions such as carbonylation, hydroformylation, reduction, oxidation, epoxydation
and hydrolysis.[50-55]

Schiff bases derived from thiosemicarbazide and their metal complexes are of
great significance for their pharmacological properties such as antibacterial,
antifungal, antitumoral, antiviral and anticancer.[56-62] The schiff base,
[63]
thiosemicarbazones have been used for the analytical determination of metals .

Ruthenium thiosemicarbazones have been found to be very efficient catalyst

in the oxidation of alcohols and alkenes.[64] Palladium thiosemicarbazones were used

as catalyst in microwave promoted Suzuki Miyaura cross-coupling rections.[65]

7
 Chapter-I

1.3. 5 Biological field :

Transition metal complexes of schiff base ligands are useful for preventing
superoxide mediated cell damage and for treatment of inflammatory disorders in
[66]
mammals particularly in humans. Technetium complexes with Schiff base and
phosphate coordination have been used as myocardial perfusion imaging agents.
Some complexes were choosen for further imaging development based on myocardial
uptake, rapid blood and liver clearances. [67] Silver complexes in oxidation state (I)
showed inhibition against C. mosaic virus, Glycine salicyaldehyde Schiff base Ag(I)
complex, gave effective results up to 74 % towards C.mosaic virus.

Fungicidal and bactericidal activity of transition metal chelates of Schiff bases

derived from physiologically active dehydroacetic acid was studied by some
workers.[68]

1.4 Literature survey of previous related studies of ligands :

The literature survey reveals that, scope of coordination chemistry is vast .The
new horizons of this chemistry extend it’s tentacles to various interdisciplinary fields.
Since the time of Alfred Werner, the coordination compounds attracted many
workers. The development of numerous newer organic chelating agents that can
coordinate with metal ions has opened up a broad scope to a research scientist in
synthetic field. An enormous amount of work has been done on metal complexes both
in solution and solid state in the last few decades. Because of their excellent chelating
properties, and diverse structural features, the Schiff bases have been used extensively
in the synthesis of metal complexes and contributed to a greater extent for the
development of coordination chemistry. Since transition metal ion, in particular, form
many stable complexes that too with Schiff base ligand, the scientist have ventured
into the detailed study of transition metal Schiff base complexes with the help of
various physicochemical techniques.

Number of metal chelates were synthesized in last few decades using variety
of Schiff bases due to their great flexibility in structure. It is well known that Schiff
bases are important compounds because of their wide range of biological activities
and as being ligands in conjugation with transition metal based compounds display
diverse structural features and in some instance exhibit interesting reactivates,
bacteriostatis and photoluminescence.[69-70] Generally, Schiff bases are insoluble in

8
 Chapter-I

water. Schiff bases obtained by condensation of ethylene diamine or

triethylenediamine with acetylacetone are reported to dissociated in aqueous
solutions. [71]

Many metal complexes of naturally occurring porphyrins, corrins and

pthalocynins have been investigated because of their potential as dyestuff or
pigments. A schiff base complex is of great importance in enhancing various
industrial applications and in a number of biological processes such as photosynthesis
and dioxygen transport.[72-73]

In view of the above mentioned facts and our continued interest in the
synthesis of novel Schiff’s base ligands based on DHA and their metal complexes, it
was thought worthwhile to synthesize new Schiff bases and their metal complexes and
to investigate bonding properties, structural aspects, thermal decomposition, spectral
characteristics and microbial activity.

1.4.1 Heterocyclic chemistry :

Heterocyclic chemistry deals exclusively with the synthesis, properties and

applications of heterocyclics especially vital to drug design. A cyclic organic
compound containing all carbon atoms in ring formation is referred to as carbocyclic
compound. If at least one atom other than carbon forms a part of ring system then it is
designated as a heterocyclic. The chemistry of heterocyclic compounds is as logical as
that of aliphatic or aromatic compounds, depending on their electronic constitution.
Their study is of great interest both from the theoretical as well as practical
standpoint. Heterocyclic compounds are widely distributed in nature and are essential
to life in various ways.[74] Compounds such as alkaloids, antibiotics, essential amino
acids, vitamins, hemoglobin, hormones and a large number of synthetic drugs and
dyes contain heterocyclic ring systems. A knowledge of heterocyclic chemistry is
useful in the synthesis and as well as in the drug metabolism. Heterocyclic
compounds have a great applicability as drugs because, they have specific chemical
reactivity and provide convenient building blocks to which biologically active
substituent’s can be attached.

1.4.2 Importance of DHA :

Literature survey reveals that many organic compounds in particular

heterocyclic aromatic compounds are physiologically active. Number of heterocyclics

9
 Chapter-I

like benzoxazole, benzimidazole, benzothiazole are reported to possess a variety of

physiological activity such as fungicidal, insecticidal, antimicrobial, anticonvulsant
and anesthetic properties.

In recent years, the design, synthesis and structural characterization of schiff

base complexes derived from dehydroacetic acid have continued interest, not only
because they can be useful models for understanding the nature of complexes of
biological relevance but also due to their interesting, structural and magnetic
properties. Transition metal complexes of dehydroacetic acid have shown antifungal
properties more active than either dehydroacetic acid alone or the pure inorganic salts.
Dehydroacetic acid was discovered by Geuther in 1866. In addition, the derivatives of
DHA are well known to possess potential anti-fungal and anti-microbial properties
owing to promising chelating properties, A large number of Schiff’s bases containing
DHA moiety and their metal complexes with various metal ions have already been
synthesized and found to possess good in vitro antibacterial and antifungal
activities.[75]

DHA has proved its significance in industries due to its physiological activity.
In view of this it was thought worthwhile to synthesize the Schiff bases of DHA and
their metal complexes. Dehydroacetic acid serves as a precursor for the synthesis of
large number of heterocyclic derivatives. Dehydroaceticacid and it’s salts are used as
[76]
stabilizers in cosmetic and pharmaceutical products and as preservatives and
additives in food, due to it’s fungicidal and bactericide activities. The heterocyclic
dehydroacetic acid (DHA) (1.1) [3-acetyl, 6-methyl (2H) pyran, 2, 4-(3H) dione],
which is used in the present work has an analogous structure with substituted 2-
hydroxy acetophenone (1.2)

O O O O
4 2
H 3 H 1
5 CH3 3 CH3
2 4
6
CH3 O O CH3 H
1 5

Fig. 1.1 Fig. 1.2

10
 Chapter-I

1.5 Literature survey of previous related studies of metal complexes :

In last two decades, there has been rapid growth in the field of coordination
chemistry of transition metals with bidentate ligands. The platinum group metals
(abbreviated as the PGMS) are six noble precious metallic elements clustered together
in the periodic table, in d-block.

The six platinum-group metals are ruthenium, rhodium, palladium, osmium,

iridium and platinum. They have similar physical and chemical peoperties, and tend to
occur together in the same mineral deposits. The platinum group metals have many
[77]
useful catalytic properties. They are highly resistant to wear and tarnish, making
platinum, in particular, well suited for fine jwellery. Other distinctive properties
include resistance to chemical attack, excellent high-temperature characteristics and
stable electrical properties. All these properties have been exploited for industrial
applications.[78-80]

1.5.1 Brief account complexes of platinum group metals:

a. Ruthenium (III) complexes:

Fig. 1.3

Michael Lee Branham[81] et al synthesized and characterized novel ruthenium

(II)complexes with the polydentate dipeptide, L-carnosine (2-[3-aminopropanoyl)
amino]-3- (1H-imidazole-5-yl) propanic acid). These were synthesized and
characterized by elemental analysis, conductivity measurement, magnetic
susceptibility, UV-visible, FTIR, 1HNMR spectra and thermal analysis study. The
ligand and complexes were screened for their antibacterial activities.

11
 Chapter-I

Fig. 1.4

N.Raja, R.Ram et al.[82] synthesized mononuclear ruthenium (III)complexes of

the type [RuX (EPh3) 2 (L)] (E=P or As; X=Cl or Br; L=dibasic terdentate dehydro
acetic acid thiosemicarbazones) have been synthesized from the reaction of
thiosemicarbazone ligands with ruthenium(III) precursors, [Ru X3 (EPh 3)3] (where
E=P, X= Cl; E=As, X=Cl or Br) and [Ru Br 3 (PPh 3) 2 (CH3OH)] in benzene
Mononuclear ruthenium (III) complexes of the type [Ru X (EPh3) 2 (L)] (E=P or As;
X=Cl or Br; L=dibasic terdentate dehydro acetic acid thiosemicarbazones) have been
synthesized from the reaction of thiosemicarbazone ligands with ruthenium (III)
precursors, [RuX3(EPh3)3] (where E=P, X=Cl; E=As, X=Cl or Br) and [RuBr3
(PPh3)2 (CH3OH)] in benzene. The composition of the complexes have been
established by elemental analysis, magnetic susceptibility measurement, FT-IR, UV–
Vis and EPR spectral data. These complexes are paramagnetic and show intense d-d
and charge transfer transitions in dichloromethane. The complexes show EPR spectra
at LNT which are typical of spin distorted octahedral ruthenium (III) species. All the
complexes are redox active and display an irreversible metal centered redox
processes. Complex [RuCl(PPh3)2 (DHAPTSC)] was used as catalyst for
hydrogenation of ketones in the presence of isopropanol/KOH.

N
Cl
N N

N Ru N

C C

R S NH2 NH2 S R
Cl

R=CH3, C4H9

Fig. 1.5

12
 Chapter-I

Sharma et al.[83] studied ruthenium (III) complexes with ligand bearing 2, 6-

diacetylpyridine bis (S-alkylisothiosemicarbazone) and their structures have been
studied using elemental analysis, molar conductance, magnetic moment, spectral data
(IR, 1H NMR, FAB Mass) and thermal investigations. The ligands behave as penta
coordinated and give acyclic complexes of the general formula [M(H2L)Cl2] and
macrocyclic complexes, [M(L)Cl2]Cl.H2O Which are formed by template
condensation by using β-diketones, pentagonal bipyramidal geometries are observed
for acyclic and macrocyclic complexes. In both types, complexes have been studied
by TGA techniques; conductance measurements reveals 1:1 electrolytic nature of the
complexes.

Co
N N
Ru
o o
Eph3 R
R
R1 R1

R=H,C4H4 R2=OCH3 Abbreviation=H2L1 ,H2L2.

Fig. 1.6

Krishnan Sampath et al. synthesized [84] bidentate Schiff base ruthenium (III)
complexes of type [Ru(CO)(Eph3)L] (where E=P/As; L=dibasic tetradentate Schiff
base ligand). Structural features of these complexes determined by various
physicochemical and spectral techniques. The interactions of these compounds with
CT-DNA via intercalation, investigation of antioxidative property showed that all
ruthenium (III) complexes have significant radical scavenging potencies against
DPPH radicals than ligand itself.
[85]
Kanne, Shanker et al. have studied reactions of [RuCl2(DMSO)4] with
some of the biologically active macrocyclic Schiff base ligands containing N4 and
N2O2 donor group yielded a number of stable complexes, effecting complete
displacement of DMSO groups from the complex. The interaction of tetradentate
ligand with [RuCl2(DMSO)4] gave neutral complexes of the type [RuCl2(L)] [where
L = tetradentatemacrocyclic ligand]. These complexes were characterized by
elemental, IR, 1H NMR, 13C NMR, mass, electronic, thermal, molar conductance and

13
 Chapter-I

magnetic susceptibility measurements. An octahedral geometry has been proposed for

all complexes. All the macrocycles and macrocyclic Ru(II) complexes along with
existing antibacterial drugs were screened for antibacterial activity against Gram+ve
(Bacillus subtilis, Staphylococcus aureus) and Gram −ve (Escherichia coli, Klebsiella
pneumonia) bacteria. All these compounds were found to be more active when
compared to streptomycin and ampicillin. The representative macrocyclic Schiff bases
and their complexes were also tested in vitro to evaluate their activity against fungi,
namely, Aspergillus flavus and Fusarium species.

Fig. 1.7

b. Rhodium (III) complexes :

Salim et al.[86] studied two new Schiff base rhodium (III) complexes, and
characterized by IR, 1HNMR, mass spectra and the elemental analysis. These
complexes have shown efficient catalytic activity in the hydrogenation of wide variety
of ketones to the corresponding alcohols in formic acid/triethylamine solution under
mild reaction conditions.

Fig. 1.8

14
 Chapter-I

Sharma et al[87] studied the synthetic, spectroscopic, and biological studies of

sixteen ring-substituted 4-phenylthiosemicarbazone and 4-nitrophenyl-
thiosemicarbazones of anisaldehyde, 4-chlorobenzaldehyde, 4-fluorobenzaldehyde,
and vanillin with ruthenium(III) and rhodium(III) chloride. Their structures were
determined on the basis of the elemental analyses, spectroscopic data (IR, electronic,
1 13
H and C NMR) along with magnetic susceptibility measurements, molar
conductivity and thermogravimetric analyses. Electrical conductance measurement
revealed a 1 : 3 electrolytic nature of the complexes. The resulting colored products
are monomeric in nature. On the basis of the above studies, three ligands were
suggested to be coordinated to each metal atom by thionesulphur and azomethine
nitrogen to form low-spin octahedral complexes with ruthenium(III) while forming
diamagnetic complexes with rhodium(III). Both ligands and their complexes have
been screened for their bactericidal activities and the results indicate that they exhibit
a significant activity.

Fig. 1.9

Mehta et al. studied[88] Pd(II), Rh(III) and Ru(III) complexes of

thiosemicarbazones of 5-chloro salicylaldehyde and 5-nitro salicylaldehyde and
characterized by elemental, spectroscopic (I.R, 1 H and 13C-NMR, electronic), molar
conductivity, magnetic susceptibility measurements, thermal studies and X- ray
diffraction studies. The thiosemicarbazones behave as neutral bidentates in Pd(II)
complex whereas in Rh(III) and Ru(III) complexes act as neutral tridentate. From the
analytical and spectral data, the stoichiometry of the complexes has been found to be
1:2 (metal: ligand). The Rh(III) and Ru(III) complexes have octahedral structures
while Pd(II) complex has square planar geometry. The X- ray diffraction studies
suggest orthorhombic crystal system for these complexes. The ligands and the metal
complexes have been screened for their antibacterial and antifungal activity.

15
 Chapter-I

H
C
O
N N H
H2N
C S Rh S CH
N N O
H
HC

Fig. 1.10
[89]
Chandra et al. have synthesized a novel tetradentate macrocyclic ligand
viz. 1,5,8, 13-tetraaza-2, 9-dimethyl-4,11-diphenylcyclotetradeca-2,4,9,11-tetraene
(L) and its complexes with Pd(II), Pt(II), Rh(III) and Ir(III) metal ions. These
complexes were characterized by elemental analysis, molar conductance, magnetic
susceptibility measurements, IR and electronic spectral studies. On the basis of
molar conductance and elemental analysis, the general stoichiometries of the
complexes were found to be [M(L)]Cl2 and [M (L)Cl2]Cl, where M=Pd(II), Pt(II)
and M‟=Rh(III), Ir(III). The spectral studies revealed the four coordinated square
planar geometry for Pd(II) and Pt(II)complexes and six coordinated octahedral
geometry for Rh(III) and Ir(III) complexes. In vitro, the synthesized ligand and its
metal complexes have been screened for bactericidal and fungicidal activities using
disc diffusion and food poison technique respectively, at different concentrations.
The organisms used in antibacterial investigation included Escherichia coli,
Staphylococcus aureus, Pseudomonas aeruginosa, and for antifungal investigation
Aspergillus-niger, Aspergillus-glaucus, Fusarium odum. The antimicrobial data
revealed that the metal complexes act more as bactericidal and fungicidal agents as
compared to the uncomplexed ligand and the metal salts.

Fig. 1.11

16
 Chapter-I

c. Palladium(II) complexes :

O Pd O

O Pd O

C N N C
H H

C N N C

CH3 CH3

H
H N C
C N
C N N C N
N H H

Pd Pd
H N CH
N C N N
C N N C
H H

H H
HO C N N C OH

N N
Pd Pd

C N N C
H H O O
OH
OH N N
H H

Fig. 1.12

Shukla S.N et al[90]synthesized and characterized Pd(II) complexes with

schiff bases derived from with 1,3 diaminopropane. In this communication, six
Pd(II)complexes were synthesized by condensation of salicylaldehyde/
benzaldehyde/ pyrrole-2-carboxaldehyde/ p-hydroxybenzaldehyde / isatin/ o-
hydroxyacetophenone with 1,3-diaminopropane in 2:1 molar ratio. Complexes of
these Schiff bases with Pd (II) metal were synthesized in 1:1 / 1:2 stoichiometric
ratio. The complexes were formulated as [Pd(L)] and [Pd(L)2]Cl2; where L is Schiff
base. Complexes were characterized by elemental analysis, molar conductance, UV-

Visible, FT-IR, 1H-NMR, 13C-NMR, 2D-NMR and ESI-Mass spectrometry. Schiff

bases were coordinated with metal through phenolic oxygen and azomethine-N or
 Chapter-I

by azomethine-N itself only, giving simple square planar geometry to complexes.

Complexes were tested for antibacterial activity MIC against gram- negative
bacteria E. coli and gram positive bacteria S. aureus and were found more potent
than Schiff bases and precursor reagents.Magnetic susceptibility data shows

diamagnetic behavior of the complexes. In the 13C-NMR spectra of complexes. a

signal observed at ~ δ 160.0 ppm in ligands assigned for >C=N group was
downfield shifted in all the complexes and appeared at ~ δ 163.0 ppm, confirming
the transfer of one lone pair of electron from nitrogen to metal and coordination of
azomethine-N to metal.

H H
C C
N N
R O R O
Pd Pd
R O N R
O N
C
C H
H

1.R=CH3 1.R=CH3
2.R=NEt3 2.R=NEt3
3.3,5-tert-Bu 3.3,5-tert-Bu

Fig. 1.13

Yoon Seo Uh et al.[91] have studied condensation of salicylaldehyde (2-

HOC6H4C (O) H) with allylamine afforded the unsaturated salicylaldimine,
2-HOC6H4C (H)=NCH2 CH=CH2. Similar reactivity was observed with substituted
salicylaldehydes. Further reaction of these Schiff bases with palladium acetate or
Na2PdCl4 afforded complexes of the type PdL2, whereL = deprotonated Schiff base.
The molecular structure of the parent salicylaldimine palladium complex [trans-(2-
OC6H4C(H) =NCH2CH=CH2)2Pd] was characterized by an X-ray diffraction study
and Crystals were monoclinic, space group P21/n, a = 14.0005(9) Å, b = 7.2964(5) Å,
c = 17.5103(12) Å, β = 100.189(1)o, Z = 4.Analogous chemistry with 4-vinylaniline
also gave novel palladium complexes containing a pendant styryl group. Crystals of
[trans-(2-HOC6H4C(H)=N-4-C6H4CH=CH2)2Pd] were monoclinic, space group
P21/c, a= 13.7710(14) Å, b = 11.0348(11) Å, c = 7.8192(8) Å, β = 98.817(2)o, Z = 2.

18
 Chapter-I

Fig. 1.14
[92]
Sergey M. Borisov et al. studied new phosphorescent red light-excitable
Platinum (II) and Palladium (II) complexes with Schiff Bases and concluded that new
Pt(II) and Pd(II) complexes with donor−acceptor Schiff bases are conveniently
prepared in only two steps. The complexes efficiently absorb in the red part of the
spectrum (ε > 105 M−1 cm−1) and show moderate to strong room-temperature
phosphorescence in the near-infrared (NIR) region. Particularly, Pt(II) complexes
possess phosphorescence, quantum yields (Φ) of ∼10%, but the emission of the
respective Pd(II) complexes is less efficient (Φ ≈ 1%−2%).The complexes exhibit
solvatochromic behavior, in which the absorption and emission spectra shift
bathochromically in polar solvents. The Pt(II) complexes are embedded in
polystyrene to produce oxygen-sensing materials. The Pd(II) and Pt(II)complexes are
demonstrated to be efficient sensitizers in triplet−triplet based up conversion systems.
Br

HC
O
O S N Ph
N
Ph N Pd Ph
N
Ph N S O N O
H
CH

Br

Fig. 1.15

Mehmet GULCAN et al.[93]studied platinum complexes of new Schiff base,

{1-[(5-bromo-2-hydroxy-benzylidene)-amino]-4-phenyl-2-thioxo-1,2-dihyro-

19
 Chapter-I

pyrimidin- 5-yl}-phenyl-methanone which was synthesized from N-amino

pyrimidine-2-thione and 5-bromsalicylaldehyde. Metal complexes of the Schiff base
were prepared from acetate salts of Cu(II), Ni(II), Co(II), Pd(II), and PtCl2 in
methanol. The chemical structures of the Schiff base ligand and its metal complexes
were confirmed by spectroscopic analysis. All of the compounds were evaluated for
their antimicrobial against 4 grampositive bacteria, 1 gram-negative bacterium, and 3
yeast strains. The Schiff base and the Cu(II) and Co(II) complexes showed good
biological activity against all tested bacteria and yeast strains.

d. Platinum (IV) complexes :

N H

H C
N
Pt
O O

Fig. 1.16
[94]
C.Shijutal studied the platinum complexes of Schiff base ligands derived
from 4-aminoantipyrine and characterized by elemental analysis, mass, 1H NMR, IR,
electronic spectra, molar conductance, and powder XRD. The structure of the metal
complex was confirmed by a single crystal XRD analysis. The Schiff base crystallized
in the triclinic, space group P-1 with a=7.032(2)Ǻ, b=9.479(3)Ǻ, c=12.425(4)Ǻ,
α=101.636(3)°, β=99.633(3)°, γ=94.040(3)°, V=795.0(4)Ǻ(3), Z=2, F(000)=352,
Dc=1.405 mg/m(3), µ=0.099 mm(-1), R=0.0378, and R=0.0967. The spectral results
show that the Schiff base ligand acts as a bidentate donor coordinating through the
azomethine nitrogen and the carbonyl oxygen atoms. The geometrical structures of
these complexes are found to be square planar. Antimicrobial studies indicate that
these complexes exhibit better activity than the ligand. The anticancer activities of the
complexes have also been studied towards human cervical cancer cell line (HeLa),
colon cancer cells (HCT116) and epidermoid carcinoma cells (A431) and it was found
that the [Pt(L3)Cl2] complex is more active.

20
 Chapter-I

CH3

HC CH
O OH O
N N
Ph N N Ph
Pt
N O O N Ph
Ph
H
Cl Cl

Fig. 1.17

Mehmet Sonmez et al.[95] studied Palladium(II) and platinum(II) complexes of

a symmetric Schiff base derived from 2,6,diformyl-4-methylphenol with N-
aminopyrimidine and reported that the mononuclear structure of the complexes was
confirmed on the basis of elemental analyses, magnetic susceptibility, IR, UV–Vis,
NMR, DTA/TGA and API-ES mass spectral data. The interaction of these metal
complexes with fish sperm double-stranded DNA (dsDNA) was studied
electrochemically based on the oxidation signals of guanine and adenine. Differential
pulse (DP) voltammetry by using renewable pencil graphite electrode was employed
to monitor the DNA interaction at the surface or in solution. The results indicate that
Pd(II) and Pt (+2) complexes with Schiff base ligand having pyrimidine rings strongly
interacted with DNA.

Fig. 1.18

Elena M. Lazic et al.[96]studied platinum complexes and reported that the

present study describes the synthesis and anticancer activ-ity of novel octahedral Pt
(IV) complexes with cyclohexyl function-alizedethylenediamine-N,N’-diacetate-type
ligands. Molecular mechanics calculation and density functional theory analysis
revealed that s-cis is the preferred geometry of these Pt (IV) complexes with

21
 Chapter-I

tetradentate-coordinated (S,S)-ethylenediamine-N,N’-di-2-(3-cyclohexyl) propanoate.

The viability of cancer cell lines (U251 human glioma, C6 rat glioma, L929 mouse
fibrosar-coma, and B16 human melanoma) was assessed by measuring mitochondrial
dehydrogenase activity and lactate dehydrogen-ase release. Cell-cycle distribution,
oxidative stress, caspase ac-tivation, and induction of autophagy were analyzed by
flow cy-tometry using appropriate fluorescent reporter dyes. The cyto-toxic activity of
novel Pt(IV) complexes against various cancer cell lines (IC50 range: 1.9–8.7 mm)
was higher than that of cis-platin (IC50range: 10.9–67.0 mm) and proceeded through
com-pletely different mechanisms. Cisplatin induced caspase-depen-dent apoptosis
associated with the cytoprotective autophagic response. In contrast, the new
Pt(IV)complexes caused rapid, caspase-independent, oxidative stress-mediated non-
apoptotic cell death characterized by massive cytoplasmic vacuolization, cell
membrane damage.

e. Iridium (III) complexes:

Abdul Hamid et al.[97] synthesized and characterized iridium

hydromeltallated-Imine complexes and reveals that I.R., 1H and 31
P NMR spectra of
the solution of [IrHCl (X-benzylidene) (Y-pyridine) (PPh3)2] and [IrHCl(X-
benzylidene) (Y-thiazole) ((PPh3)2] in CDCl3 show that the hydride resonances
absorb in the range of δ(-) 14.60 – (-) 15.04 ppm for pyridine complexes and in the
range of δ (-) 15.46 – (-) 19.98 ppm for imidazole’s complexes. The hydride complex
formation strongly suggest that oxidative addition of CH=N to iridium take place by
=C-H bond activation of the imine ligand. The disposition of the hydride ligand was
31
inferred as trans to a N-donor ligand. The P-chemical shifts for the phosphorous
atom bonded to iridium falls in the range of δ13.20 – 16.14 ppm.

Fig. 1.19

Monika Tyagi et al.[98]synthesized Iridium metal complexes derived from 2,6-

diacetylpyridine (bisthiosemicarbazone).The coordination compounds of Ir(III) metal
ions with a Schiff base ligand i.e. 2,6-diacetyl pyridine bis (thiosemicarbazone) have

22
 Chapter-I

been synthesized and characterized by elemental analyses, molar conductance,

magnetic susceptibility measure-
measure ments, IR, NMR and electronic spectral
pectral studies. On
the basis of molar conductance and elemental analysis the complex were found to
have composition [M’(L)Cl]Cl2, where M = Ir(III). The spectral studies reveal that
the complexes possess monomeric composition. Ir(III) posses six coordinat
coordinated
octahedral geometry. The ligand field parameters were calculated using various
energy level diagrams. In vitro synthesized compounds and metal salts have been
tested against some species of plant pathogenic b.

M=Ir, Rh

Fig. 1.20

1.6 Aim of the present investigation :

The literature survey reveals that the most of the work which have been
reported is related the Schiff bases derived from DHA and aliphatic, aromatic amines
and related compounds with first series transition elements, however, a little work is
reported on PGM.

With this aim in mind, the present study deals with the synthesis of solid
complexes of Ruthenium, Rhodium, Palladium, Platinum and Iridium metal ion
ions with
Schiff bases derived from DHA with the following aromatic and aliphatic amine.

1) 2-amino
amino phenol

2) 2-amino-5
5-methyl phenol

3) 2-amino-4Nitro
4Nitro phenol

4) 2-amino-4
4-chloro phenol

5) 1,3 diaminopropane
 Chapter-I

The characterization of Schiff bases and their corresponding metal complexes

were carried out using physicochemical techniques involving elemental analysis,
molar conductance, thermal, spectral and x-ray powder diffraction analysis and
studied antimicrobial activity, of these ligands and their metal complexes.

R'

OH HO O
OH N O

H OH
O N N O

O O

OH N

H OH

O O

R’=CH3,R= H,Cl,NO2.

Fig. 1.22

24
 Chapter-I

1.7 References :

1. Huhey, J. E. "Inorganic chemistry", Haper & Row, New York (1983).

2. Rossoti F.J.C and “The determination of stability constants” Mcgrawgrill

book co; New York (1961).

3. Brack, W.H K.A.; Jensen, C.K.; Jorgensen and Kauffman G.B., "The origin
and dissemination of the ligand in chemistry" Ambix 27(1981), 171.

4. Bethe, H. Ann.physik, 5 (1929), 133.

5. Van vleck J. H ., Z.physik, 73 (1931),565.

6. Sagar B.A.; Micheal, J.P & Hanclock , R. D. J.Inor.chim.Acta, 77 (1983),163.

7. Weighrdt, K.; Bossek, U.; Guttmann, U.; Weiss, J.; Naturefresh, Z. and Teli,
B., Inor.Chem 38 (1983,81)

8. Kabachink, M.I.; Medvad, T.Ya.; Shcherbakov B.K.; Sinyavskaya, F.I.;

polikarpov, Y. M.; Yatsimirskii, K. B., Russ. J.Inorg. chem. 30 (1985), 1463.

9. Vaira, M.D.; Mani, F.; Stoppioni, P., Inoganic.chem.acta, 303 (2000), 61.

10. G. N. Lewis, J. Am. Chem. Soc., 38 (1916), 762

11. Pauling, L., “The nature of Chemical bond”, 3rd Edn, Cornell University
press, Ithaca, New York, 161 (1960).

12. Pauling, L., “The nature of Chemical bond”, 3rd Edn, Cornell University
press, Ithaca, New York, 162 (1960).

13. Bethe, H., Ann. Physik., 5 (1929), 133.

14. Van Vleck J. H., Z. Physik., 73 (1931), 565.

15. Rossoti F.J., “The determination of stability constants” Mcgrawgrill book co;
New York (1961).

16. Morgan K.C. and Drew, J., Chem.Soc.117,1456(1920).

17. Ashraf M.A.; Mahmood, A.; Wajid A., IPCBEE, (2011),10,1-7.

18. Meldola, R.; Kuntzen, H.S. and Brightman.R., J. Chem.Soc; 97,456(1910).

19. Holm, R. H.; Prog. Inorg. Chem; 7,204 (1966). Gffermann, P.W. and warner,
H., J. Prakt Chem; 159,313(1943).

20. Schiff A. Ann. 151, 186 (1869).

25
 Chapter-I

21. Schiff H. Ann. 151, 211 (1869).

22. Melson, G. A. Eds, Coordination chemistry of Macrocyclic compounds;

Plenum New York, (1979).

23. Izatt, R. M. and christensen, J.J., Eds. ''Synthesis of Mcrocycles the Design
of selective complexing agents, progress in macrocyclic chemistry; willey
interscience''; New York, (1987),Vol.3.

24. Lindoy, L.F. "The chemistry of macrocyclic ligand complexes"; Cambridge

university press; Cambridge (1989).

25. Dally, K., In synthetic multidentate Macrocyclic compounds; Izatt,R.M.;

Christensen, J.J .;Eds. Academic press; New York, (1978).

26. GuptaY.K.; Agrawal S.C.; madnwat S.P.; Ram Narain, Res. J.chem.sci,2(4)
68-71,April (2012).

27. Parekh J. Inamdar P.; Nair R.; Baluja S.; chanda S. J. serb.chem.soc ; 70,1155-
1161(2005).

28. Sinha D.; Tiwari A K.; Sing S.; Shukla G.; Mishra P.; Chandra H.; Mishra A
K.Eur.J.med.chem;43,160-165, (2008).

29. Kumar Y.; Gupta V.; and Singh S. Journal of pharmacy Research, Elsevier, 7
(6), 491-495 (2013).

30. Houch, Zhu J.; Qiz,Zhou B.; Li M. Liu Y.; Wahan univ.J.Nat sci; 15,71-
77(2010).

31. Aggrawal N.; kumar R.; Durja P.; Rawal, D.S. J.Agric, Food chem;57,8520-
8525 (2009).

32. Adsule S.; Barve V.; Chem D.; Ahmed F.; Dau, Q.P.; Pathye, S.; Sarkar, F.H.
J.med.chem; 49, 7242-7246 (2006).

33. Elerman, Y.; Kabak, M.K.; Elmali, A. Z. Nature fresh. Jiut chem. soc, 357,
651, (2002).

34. Lions F. and Barry Aust. J. Chem., 22, 17-87 (1969).

35. Avaji, P.G.; Kumar, C.H.V.; Patil, S.A.; Shivnanada K.N. and Nagarjun, C.
Eur.J.med.chem; 44 (2009), 3552.

36. Brugsch, H.G.; J. occup .med; 7 (1965), 394.

26
 Chapter-I

37. Dash, B.; Mahapatra, P.K.; Panda, D. & Patnaik, J. M. J.Indian chem. Soc, 61
(1984)1061-1064.

38. Rao, N. R.; Rao, P. V.; Reddy, G. V.; Ganorkar, M. C. Indian J chem, 26 A
(1987) 887-890.

39. Mishra, P.; Gupta, P. N. & Shankya, A .K . J. Indian chem. Soc, 68 (1991)
539-541.

40. Manav N.; Mishra, A.K. and Kaushik, N.K. Spectrochemica acta part A :
Molecular Spectroscopy 60 A 3087-3092 (2004).

41. Abel-Surrah, A. S.; Kutteunen, M. Current Medicinal Chemistry, 13,1337-

1357 (2006).

42. Jakson, A.; Davis, J.; Pither, R.J.; Rodger, A. Inorg.Chem; 20, 3964-3971
(2001).

43. Jame, E.H.; Ellen, A.K. and Richard, L.K. “Inorganic chemistry”, Harper
Collins, Fourth Edn; 97 (1993).

44. Dwyer, F.P.; Mayhew, E; Roe, M.F. and Schilman, R. J.Cancer Res.19, 195
(1965).

45. Crim, J.A.; Petering, H.G. J.Medicnal. Chem.13, 763 (1976).

46. Frihant, E.J.; Bailer, J.C. J. Inorg.Nucl.Chem; 241, 205 (1962).

47. Kaul, Bansilal, Sandoz-Patent. Gmbh, Frg.Ger.Offin.D.E; 3413603, Al, 24

Oct; 12 (1985).

48. Leung et al; 2013; Zhong et al; 2014; Liu et al; 2014; Ma et al; 2014 and
Leung et al; (2012).

49. Mullhaupt, J. T.; Stephenson, N. A; Stephenson,P.C. and Notaro Frank; Eur.

Pat. appl. EP.711598A2, 15 May, 37 (1996).

50. Khan, M. M. T.; Halligudi, S. B.; Shukla S.; and Shaikh, Z.A.; J.Mol, Catal;
57, 301(1990).

51. Khan, M.M.T.; Halligudi S.B.; Rao, N.S.; J. Mol,Catal; 63, 137(1990).

52. Aoyama, Y.; Fujisawa, T.; Walanav, T.; Toi H. and Ogashi, H. J. Am, Chem,
Soc; 108, 943 (1986).

53. Kimura, E.; Machida R. and Kochima, M. J.Am.Chem, Soc; 106, 247 (1990).

27
 Chapter-I

54. Bhattacharya, P.K. Proc, Ind, Acad, Sci;(Chem.sci), 102.247, (1990).

55. Brown, R.S.; Zamakani, M.; Sho, J.L. J.Am, Chem, Soc; 106, 5222 (1984).

56. Patil, S.A.; Naik,V.H.; Kulkarni, A.D and Badami, P.S. (2010) Spectro

chimica Acta A ,75, 347-354.

57. Sharma, K.; Sing, R.; Fahmi, N.; Singh, R.V. (2010) Spectrochemica Acta A,
75, 422-427.

58. Al-Amiery, A.A.; Al-Majedy, Y.K.; Abdul Reazak, H. and Abood, H. (2011)
"Bioinorganic chemistry and applications", (2011), 1-6, Article ID 483101.

59. Wiecek, J.; Kovala-Demertiz, D.; Ciunik, Z.; Zervou, M. and Demertizis,
M.A. (2010), 1-9, Article ID 867195.

60. Ferraz, K.O.; Wardell, S.M.S.V; Wardell, J.L.; Louro, S.R.W and Beraldo, H.
Artenia salina, Spectrochimica Acta A, & 3, 140-145.

61. Graminha, A.E.; Bastida, A.A.; Mendes, I.C.; Teixeria, L.R. and Beraldo, H.
Spectrochemica Acta A, 69, 1227-12845.

62. Raja, N. and Ramesh, R. (2010) Spectrochemica Acta A, 75, 713-718.

63. Praveen Kumar A.; Reddy P.R. and Reddy, V.K. Jour.of The Korean Chem
Soc, 51, (2007), 331.

64. Jayabalkrishnan, C.; Kaevembu, R.and Natarajan, K. International J. of Che.

Sci. 32, (2002), 1099.

65. Kostas, I.D.; Heropoulos, D.A.; Kovala-Demertzi, D.; Yadav, P.N.; Jasinki
J.P.; Dermertiz, M.A.; Andreadaki, F.J.; Thanah, V. Petit, G. A. J.Tetrahedron
Letters, 47, (2006), 4403.

66. Sttamler, J.S.; Crapo, J.D.; Fridovich, I.; Day, B.J. and Sarvaey, D.S. Patent
CA-1, Pct. Appl. WO. 9639409A1, 12 Dec; 66 (1996).

67. Marmion, M.E.; Woulfe, S.R.; Neumann, W.L; Nosco, D.L. and Deutsch, E.
Nuclear Med. Bio; 26 (7), 755-770. Els. Sc. Inc. (1999).

68. Agarwal, R.C.; Prasad, B. and Yadav, B.N. J. Inorg. Met Org.Chem, 23, 1061
(1993).

69. Guo H.F.; Zhao X.; Ma DY, Xie Ap, Shen WB. Transition Metal chemistry
(.2013); 38 (3): 299-305.

28
 Chapter-I

70. Abou-melha K.S. Journal of co-ordination chemistry ( 2008); 61 (3): 2053-

2067.

71. Tzeng B. C.; Chem, S.C.; Chan, MCW, Chem, C.M.; Cheurg, K.K. Pengsm.
Inorganic chemistry, (2004); 40 (26): 6699-6704.

72. Raper, E.S. Cord. Chem. Rev; 165, 475-567 (1997).

73. Carceli, M.; Kumar, A.; Dwivedi, J.; Singh, R. International Journal of
pharma Sciences and research, 4, 66-77 (2013).

74. Kogan, V.A.; Levchenko, S.I.; Popav, L.D.; Shcherbakov, I.A. Russian
Journal of general chemistry, 79, 2767-2775 (2009).

75. Miyakado, M.; Inoue, S.; Tambe, Y.; Watabe, K.; Ohno, N.; Yoshioka, H.;
Mabry, T. J. Podophytham pelratum L. Chem, Lett.; 1539-1542.

76. Kabra, J. J.; (1984)., J. Am. Chem, Soc, 61, 397-403.

77. Reenner Schlamp, G.; Kleinwachter, Dorst, I.; Uschow, E.;L.; Tews, H.M. P.
Diehl, M et al. Russian Journal of general chemistry 72 (2002).

78. Harris, D. C.; Cabri L. J. (1991) Inorg.chem.commun.5- 537.

79. Rollinson, Hugh. (1993) Longman Scientific and Technical. ISBN 0-528-
06701-4.

80. Weeks, M.E. (1968) Journal of chemical Education. PP. 385-407.

81. Lee, M.B.; Sing, P.; Bisethy, K., (2011), 16, 10269-10291; doi-1033901
Molecules 16210269.

82. Raja, N.; Ramesh, R. Biomolecular Spectroscopy, Elseiver 17 Nov. (2009).

83. Sharma,V. K.; Shrivastava, A. Indian J.chem, Vol. 46A, December (2007),
1963-1968.

84. Sampth, K.; Subhiyam, S. Taylor and Francies Group, LLC, 43, 1279-1288,
(2013).

85. Shanker, K. R.; Rohini, V.; Ravindera, P.M.; Reddy, Yen-Peng Ho,
Spectrochimica Acta Part A., 73 (2009) 205.

86. T.Al.-Salim, Journal of scientific Research 2 (3), 501-511 (2010).

29
 Chapter-I

87. Sharma, K.V.; Shrivastava, S.; Shrivastava, A. Hidwi Publishing Corporation

Vol. (2007), article ID. 68374, DOI: 10/ 155/2007/68374.

88. Mehta, B.; Shaikh, J.A. J. Ind. Concil Chem, Vol. 26, No. 1, (2009), PP.1-6.

89. Chandra, S.; Tyagi, M. and Agrawal, S. J. Saudi Chem. Soc., 15 (2011) 49.

90. Shukla, S.N.; Gaur, P. Inter. J. of Basic and Applied Chemical Sciences
(2015), Vol. 5 (1) Jan.-March, PP.18-28.

91. Yoon-Seo Uh.; Haiwen, Zong, Bull.Korean Chemical Soc. (2004), Vol. 25
Nov.7.

92. Seray, Borisov, M.; Robert Saf, R.; American chem. Soc. (2013), 52, 1206-
1216.

93. Mehmet, S.; Metin, C.; Yavuz, Yardim.; Eur. Jour. of Medc. Chemistry,
Vol.45, Issue 9, Sept (2010), Pages 4215-4220.

94. Jose M.Vila; Teresa M.T.; Pereira; Juan, M. Ortigueire, J.Org.Chem. (1998),
P. 93-101.

95. Mehmet, G.; Mehmet SONMEZ. Turk. J. Chem, 36 (2012), 189-200. doi:
10.3906/Kim-1104-2.

96. Elena M.; LjubicaVucˇic´evic´.; J. Sabo *DOI : 10.1002/c mdc.201000058. J.

Med. Chem (2010), 5, 881 – 889.

97. Hamid, A.; Isaygh, A.; Jehnan, A. H.; Asian Journal of Science & Technology
Vol.5, Issue 11, PP. 647-652, November, (2014).

98. Tyagi, M.; Chandra, S.; Open Journal of Inorganic Chemistry, (2012), 2, 41-
48.

*****

30