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1
CHAPTER-I
Introduction
Literature Survey
Aim and Significance of the present study
2
“THE EVER INCREASING APPLICATIONS OF METAL
COMPLEXES IN VARIOUS FIELDS OF SCIENCE IS THE DRIVING
FORCE FOR THE RESEARCH AND DEVELOPMENT IN
COORDINATION CHEMISTRY”
Coordination compounds are the inorganic salts formed by the
combination of two or more simple compounds in stoichiometric ratio. The
first theory regarding coordination compounds was proposed in 1893 by Alfred
Werner who is the Father of Coordination Chemistry. He received Noble
prize for his work on coordination chemistry in 1913. Coordination compounds
containing at least one complex ion in which a central metal ion is surrounded
by certain number of ions or molecules through coordinate bonds, study of
these types of compounds are called as coordination chemistry.
Today coordination chemistry comprises a large body of inorganic
chemistry research. It is mainly the chemistry of metal complexes and has
fascinated and inspired the chemists all over the world. There is an ever
increasing academic, commercial and biochemical interest on the metal
complexes of organic chelating ligands. This has resulted in the emergence of
allied fields like organometallic chemistry, homogenous catalysis and
bioinorganic chemistry. Among the chelating ligands, Schiff bases have
attraction the chemists due to ease preparation and complexation. Although
there has been a welcome renaissance in inorganic chemistry after Werner’s
time [1], the base tenants of this theory has not been discarded but has been
refined and extended greatly. Realisation of the involvement metal complexes
in biological systems has also helped to sustain a live interest in metal
complexes of multidentate ligands. Multidentate ligand systems such as Schiff
bases, azo compounds, hydrazones, etc., form unique class of compounds.
Among these compounds, Schiff bases and their metal complexes occupy an
outstanding role in the development of coordination chemistry, because of the
synthetic proclivity, structural diversion and varied applications in different
fields. Hence, it is quite fascinating to discuss the salient features of this class
of compounds, which form the part of this investigation.
3
The list of noble prizes on Coordination chemistry is significant and
shows the manifestation of Coordination chemistry into various fields of
science.
Nobel Prizes on Coordination Chemistry
Year Name Worked on
1912 Victor Grignard Grignard's reagents.
1913 Alfred Werner The area on the nature of bonds of atoms in molecules in inorganic chemistry.
1915
1918
Rihard Vilshtetter
Fritz Haber
The area of pigments in plant world especially chlorophyll.
The synthesis of ammonia.
1930 Hans Fisher Investigation of construction of hemine and chlorophyll.
1963 Karl Ziegler Giulio Natta Discovery of isotactic polypropylene.
1964 Doroti Meri Kroufut Hodzkin Determination of structures of biologically active substances by X-Rays.
1973 Ernst Otto Fischer &
Geoffrey Wilkinson
Organometallic chemistry.
1987 Donald James Cram, Jean-Marie Lehn and Charles J. Pedersen
Elaboration and applications of molecules having structurally-specified interactions of high selectivity.
2001 William S. Knowles, Ryoji Noyori and K. Barry Sharpless
Research in pharmaceutical industry: creation of chiral catalysts for redox-reactions.
2005 Yves Chauvin, Robert H. Grubbs, Richard R. Schrock
The development of the metathesis method in organic synthesis.
4
A new era has started in coordination chemistry since 1869 after Schiff’s
elegant synthesis of azomethane complexes of copper (II) from preformed
metal, salicylaldeyde and primary amine. Schiff base is formed as a
condensation product of primary amine with carbonyl compounds. This was
first reported by Schiff [2], which contain the >C=N- group which is also
called azomethane, imine or anil. The >C=N- group in combination with more
such groups or others like phenolic –OH or amino groups can effectively form
metal complexes. The Schiff base ligands and their complexes have significant
importance in chemistry and every year a number of reports are published on
the preparation of these compounds and their application in chemical reactions
[3]. Schiff bases of aliphatic aldehydes are relatively unstable and readily
polymerizable, while those of aromatic aldehydes having effective conjugation
are stable. In general, aldehydes react faster than ketones in condensation
reactions, leading to the formation of Schiff bases as the reaction centre of
aldehyde are sterically less hindered than that of ketone. Furthermore, the extra
carbon of ketone donates electron density to the azomethine carbon and thus
makes the ketone less electrophilic compared to aldehyde.
The Schiff base compounds and their complexes are widely applied in
enantioselective cyclopropanation of styrenes [4],asymmetric addition of
cyanide to aldehydes [5], asymmetric aziridination of olefins [6],
enantioselective epoxidation [6,7], regio- selective ring opening of epoxides [8]
and as a membrane in ion selective electrode [9–13]. The metal complexes of
Schiff bases also finds applications in versatile catalytic reactions for organic
synthesis [14-17], degradation of organic substances [18], in
radiopharmaceuticals [19], their ability to reversibly bind oxygen [20] and
photo chromic properties [21]. Schiff base metal complexes have also found
greater applications in biological field.
Schiff bases have been reported to exhibit a variety of biological actions
by virtue of the azomethine linkage, which is responsible for various
antibacterial, antifungal, herbicidal, clinical and analytical activities [22–25].
Recently, there has been tremendous interest in studies related to the interaction
5
of transition metal ions with nucleic acid. because of their relevance in the
development of new reagents for biotechnology and medicine [26]. There has
also been substantial interest in the rational design of novel transition metal
complexes, which bind and cleave duplex DNA with high sequence and
structure selectivity [27-29].Various studies have shown that, the presence of
lone pair of electron on trigonally hybridised nitrogen atom of the azomethane
group >C=N- is of fundamental chemical and biological importance
[30].Biological significance of Schiff base complexes have been reported
widely in literature [31]. Many Schiff bases have been used as analytical
reagents, corrosion inhibitors, flocculants, medicines and therapeutic agents
[32-33].Many Schiff Base complexes of metals possess antitoxic, cytotoxic,
antimicrobial and antibacterial activity [34-35]. Some Schiff base complexes
have been reported to be active against leukemia and also exhibit antitumor
activity [36].
Some Schiff base complexes have been reported to possess therapeutic
activities [37-40] and found to possess anti-inflammatory, antipyretic,
analgesic, cardioscopic and diuretic action. The use of Schiff base complexes
in nuclear medicine also has been reported recently [41]. Some Schiff bases
show retardation in root development in detached cabbage leaves [42]. Copper
azomethane complexes find application as pigments. There is suggestive
evidence that, the visual pigment rhodospin contains azomethane linkages [43].
Schiff bases have been reported to exhibit a variety of biological actions
by virtue of the azomethine linkage, which is responsible for various
antibacterial, antifungal, herbicidal, clinical and analytical activities [44–47]. It
is known that, chelation of metal ions with organic ligands acts synergistically
to increase their biological activities [48]. Recently, there has been tremendous
interest in studies related to the interaction of transition metal ions with nucleic
acid because of their relevance in the development of new reagents for
biotechnology and medicine [49]. There has also been substantial interest in the
6
rational design of novel transition metal complexes, which bind and cleave
duplex DNA with high sequence and structure selectivity [50-52].
Coumarin
Coumarin (2H-chromen-2-one, 2H-1-benzopyran-2-one) is structurally
the least complex member of a large class of compounds known as
benzopyrones and also coumarins are among the best known oxygen
heterocyclics with a d-lactone ring which comprise a very large class of
compounds found throughout the plant kingdom [53-55]. The biological
activities of coumarin derivatives are multiple and include antithrombotic [56],
antimicrobial [57], antiallergic [58], anti-inflammatory [59], antitumor [60] and
anticoagulants [61]. Derivatives of coumarin are known to possess significant
antifungal as well as antibacterial properties. Many of the coumarins present in
plants and also their synthetic analogues, have been reported to be good
antifungal and antibacterial agents [62-69]. Preliminary structure– activity
relationship studies have shown that, the presence of hydroxyl or carboxylic
groups on the coumarin nucleus is necessary for antimicrobial activities [70].
The presence of coumarin nucleus in the antibiotics, such as novobiocin,
clorobiocin and coumermycin A1 were identified over forty years ago. But, the
use of these antibiotics has been limited due to their poor water solubility, low
activity against Gram-negative bacteria and the rapid emergence of resistance
[71-47].
Coumarins are nowadays an important group of organic compounds that
are used as additives to food and cosmetics, optical brightening agents and
dispersed putrescent and laser dyes [72-74]. The derivatives of coumarin
usually occur as secondary metabolites present in seeds, roots and leaves of
many plant species. Their function is far from clear, though suggestions include
waste products, plant growth regulators, fungi stats and bacterio stats. It is
therefore of utmost importance that, the synthesis of coumarin and its
derivatives should be achieved by a simple and effective method. The synthesis
of this heterocyclic nucleus is of current interest. Coumarins have been
7
synthesized by several methods including Von Pechman, Knovenagel and
Reformatsky reactions.
However, renewed interest in these antibiotics has arisen following the
discovery that, they are potent catalytic inhibitors of DNA gyrase.
Additionally, these antibiotics have been shown to be active against Gram-
positive bacteria, especially against Methicillin-resistant Staphylococcus
aureus (MRSA) [75]. Further, derivatisation of novobiocin, clorobiocin, and
coumermycin A1 has allowed for the production of novel coumarin antibiotics
displaying excellent inhibition of DNA supercoiling by DNA gyrase B and
good antibacterial activity against vancomycin, teicoplanin and novobiocin
resistant Enterococci species [76-78].
A part from the biological significance, Schiff bases and their metal
complexes find applications in various other fields. Some aromatic Schiff bases
have been used as stabilizers [79] for a wide variety of compounds which
include jet fuels, fuel oils, lubricating oils etc., Schiff bases have been
incorporated in several polymers [80] to produce certain desirable
characteristics in the final products. This includes superconducting property,
resistance towards heat, light and oxidation, hardness and vulcanisation.
Certain Schiff base complexes of metals have been used for the catalytic
oxidation of ascorbic acid and cysteine. Some Schiff base complexes have been
used in the catalytic decomposition of hydrogen peroxide [81]. Aromatic Schiff
bases and their metal complexes are found to have strong catalytic influence
[82] on reactions like oxidation, decomposition and polymerisation. Many
Schiff base complexes find use as dyes and as electrographic materials. In
view of such a fascinating structural and biological features of coumarins, in
the present study hydroxy substituted formyl coumarins have been utilized for
the synthesis of various Schiff bases.
Isatin
Isatin (1H-indole-2,3-dione) was first obtained by Erdman and Laurent
in 1841 as a product from the oxidation of indigo by nitric and chromic acids.
8
Isatin and its derivatives have been extensively used as versatile reagents in
organic synthesis: to obtain heterocyclic compounds and as raw material for
drugs [83-84], some synthetic oxindole based compounds have been developed
as anticancer, anti-HIV or antimicrobial agents [85]. The synthetic versatility of
isatin has stemmed from the interest in the biological and pharmacological
properties of its derivatives. In recent years, there has been enhanced interest in
the synthesis and characterization of transition metal complexes containing
Schiff bases as ligands, due to their importance as catalysts for many reactions
[86-87]. Tetradentate Schiff base complexes of isatin are also very important
for various biological applications, [88-89] namely antibacterial, antiviral,
antimalarial, antitumour, [90-91] etc., In addition, anti-inflammatory activity
has also been reported for these complexes [92-93]. The complexes of
transition metals with Schiff bases show better biological activity than the free
ligands [94]. Although there is a wealth of information concerning transition
metal complexes with isatin Schiff bases [95-97] it is largely confined to the
first row metals, such as copper, iron, cobalt and nickel [98-99].
Triazole
Substituted 1,2,4-triazoles are among the large number of heterocyclic
compounds that have received the most attention during the last two decades as
potential antimicrobial agents. They are associated with diverse biological
activities such as fungicidal, antimicrobial, antiviral activities etc. [100-104].
The 1,2,4-triazole nucleus has been incorporated into a wide variety of
therapeutically interesting drugs, including H1/H2 histamine receptor blockers,
Cholinesterase- active agents, CNS stimulants, antianxiety agents and sedatives
[105]. Mercapto derivatives of substituted 4-amino-l,2,4-triazoles are
particularly interesting as complexing agents due to the presence of four
potential donor atoms (three nitrogen and one sulphur), consequently many
metal derivatives of ligands of this type have been prepared [106-110]. Schiff
bases of o-phenylenediamine and its complexes have a variety of applications
9
including biological [111], clinical [112] and analytical [113]. Earlier work has
shown that, some drugs exhibited increased activity when administered as
metal chelates rather than as organic compounds [114-115] and that the
coordinating possibility of o-phenylenediamine has been improved by
condensing with a variety of carbonyl compounds. Also the primary amines are
known as better condensing agents.
Survey of the Previous Work
S. U. Rehman et al., have synthesized the Schiff bases derived from 3-
formyl-4-chlorocoumarin and heteroaromatic amines/hydrazides [116]. The
Co(II), Ni(II), Cu(II) and Zn(II) complexes of these Schiff bases have been
synthesized, stpectroscopically characterized and screened for their in-vitro
antibacterial activity against E. coli, K. pneumoniae, P. mirabilis, P.
aeruginosa, S. typhi, S. dysenteriae, B. cereus, C. diphtheriae, S. aureus and S.
pyogenes bacterial strains and for in -vitro antifungal activity against T.
longifusus, C. albicans, A. flavus, M. canis, F. solani and C. glaberata.
From our laboratory, G.B.Bagihalli et al., have studied the Co(II),
Ni(II),Cu(II) and Zn(II) complexes with Schiff bases derived from 3-
substituted-4-amino-5-mercapto-1,2,4-triazole and 8-formyl-7-hydroxy-4-
methylcoumarin [117] have been reported. These complexes have been
characterized on the basis of elemental analyses, spectral, magnetic and thermal
studies.
N
NN
S
N
N
N N
R S
N
CHO
O
OCH3OH2
OH2
R
MCH
OO
CH3
OM
OH2
OH2
O
n
R=H, CH3, C2H5 and C3H7
10
G.B.Bagihalli et al., have reported the complexes Co(II), Ni(II) and
Cu(II) with Schiff bases derived from 3-substituted-4-amino-5-hydrazino-
1,2,4-triazole and 8-formyl-7-hydroxy-4-methylcoumarin [118]. These
complexes have been characterized on the basis of elemental analyses, spectral,
magnetic and thermal studies.
N
NN
NH
CHOO
OCH3
CH
O
CH3
ON
O
R
N
M
OH2
OH2
Very recently, series of metal complexes of Co(II), Ni(II) and Cu(II)
have been synthesized with the Schiff base derived from thiocarbohydrazide
and 8-formyl-7-hydroxy-4-methylcoumarin [120]. From our laboratory, the
structures of these complexes have been proposed by elemental analyses, molar
conductance, spectral (IR, UV–Vis, ESR and FAB-mass), magnetic, thermal
and electrochemical studies. These complexes are soluble in DMF and DMSO
and molar conductance values indicate that they are non-electrolytes.
The series of metal complexes of Co(II), Ni(II) and Cu(II) have been
synthesized with the Schiff base derived from Ortho-Phthalaldehyde and Bis-
(4-Amino-5- Mercapto-1,2,4-Triazole-3-yl)Alkanes [121]. The structures of the
complexes have been proposed by elemental analyses, molar conductance,
spectral (IR, UV–Vis, ESR and FAB-mass), magnetic, thermal and
electrochemical studies. These complexes are soluble in DMF and DMSO and
molar conductance values indicate that, they are non-electrolytes.
11
N N
N
N
NN
SH N
NN
S H
N
N N
SH N
N N
S H
N
( C H2)
( C H 2)
MO H2 O H2 .
n
n
o o
o o
N
N
o
o
( H 2 O)3
Karaliota et al., reported the binuclear molecules [Cu2(L)4(H2O)2], in
which the two copper atoms are bridged in pairs by four carboxylic groups of
the coumarin-3-carboxylate ligand, and are also bonded to two water molecules
[122]. Thus, each copper atom is coordinated by four oxygen atoms lying on its
basal plane and the water oxygen atom on its apex. The coordination sphere
may be completed with the Cu�Cu contact to form a distorted octahedron.
Finally, two additional water molecules complete the molecular formu
[Cu2(L)4(H2O)2]·2H2O. These two lattice water molecules per dimmer stabilize
the structure, most probably via hydrogen-bonds. An extensive hydrogen-
bonded network could account well for the insolubility of the complex.
B. S. Creaven et al., have reported the Cu(II) complexes of bidentate
coumarin Schiff bases [123]. The Schiff bases have been synthesized via
condensation of 7-amino-4-methylcoumarin with a number of substituted
12
salicylaldehydes and are characterized by IR, 1H & 13C NMR, UV-vis., and
elemental analyses. Subsequently, these ligands are reacted with copper(II)
acetate to form Cu(II) complexes. These Cu(II) complexes were characterized
by IR, UV-vis., molar conductance, magnetic properties and crystal analysis
data. The Schiff bases and their Cu(II) complexes were studied for their anti-
candida activities.
Junna Yao et al., have reported the coumarin-based podand-type ligand
and its five complexes [Ln(NO3)3L] (Ln = Pr, Eu, Gd, Tb and Er] were
synthesized. The Ln(III) ion is coordinated with ten oxygen atoms, four of
which belong to the tetradentate ligand ‘L’ and the remaining six belong to
three bidentate nitrate groups. The four ‘O’ atoms assume a half-ring shape,
and form a pentacyclic-ring-like coordination structure together with one ‘O’
atom of the nitrate. The two chelate chains are flexible and their distance and
separation angle decrease with the smallness of coordinated metal ions.
The synthetic route for the ligand ‘L’ and the lanthanide complexes
13
The pentacyclic-ring-like structure in the coordination polyhedron
Aim and Significance of the Present Research Work
In recent years, there has been lot of interest shown in the synthesis and
physico-chemical properties of transition metal complexes with substituted 1,
2, 4-triazoles. Triazoles and their derivatives have been proved to be effective
bactericides [65], pesticides [124], fungicides [125, 126] and insecticides [127,
128]. Many Schiff bases derived from either heterocyclic amines or aldehydes
have been studied for their ability to form complexes with the transition metals
[129-130].
In biological front, Coumarins have long been recognized to possess
anti-inflammatory [131], antioxidant [132], antithrombtic [133], antiallergic
[134], hepatoprotective [135], antiviral [136] and anticarcinogenic [137]
activities. The hydroxycoumarins are typical phenolic compounds and
therefore, used as potent metal chelators and free redical scavengers. They are
powerful chain-breaking antioxidants [138]. The coumarins display a
remarkable array of biochemical and pharmacological actions [139], the
antitumor effects of coumarin and its major metabolite, 7-hydroxycoumarin,
were tested in several human tumor cell lines [140]. Furthermore, cytotoxic
effects of complexes of coumarin derivatives were examined on several
neuronal cell lines [141].
14
It is in this context that, the author undertook a comprehensive research
work on the synthesis of some transition metal complexes of various bidentate,
tridentate and tetradentate Schiff bases. Thus, the aim of present research work
is to synthesize some Schiff bases derived from coumarin, triazole and isatin
etc., and to stitch them with various transition metal ions to form metal
complexes.
The Schiff bases and their metal complexes were characterized by
extensive spectroscopic and analytical methods. The structural properties of
Schiff bases have been studied by FT-IR, UV-vis., FAB-Mass, NMR (1H and 13C) and elemental analyses. Owing to the fluorescence properties of
precursors, some of the Schiff bases and their metal complexes have been
evaluated for their fluorescence properties.
X-ray crystallographic study is the most definite source of information
regarding the structure of a complex. But, due to the difficulty in obtaining the
crystals of metal complexes suitable for X-ray crystallographic study, has
rendered this method less suitable for these complexes. In such cases, a variety
of other techniques can be used with good effect and have been done in this
investigation. The structural diversities of metal complexes have been
undoubtedly proposed in the light of FT-IR, UV-vis., FAB-Mass, NMR and
ESR spectral data wherever possible or applicable, elemental analyses,
conductance measurements, magnetic measurements and thermogravimetric
analyses studies. Electrochemical behaviour of some metal complexes has been
studied by the Cyclic Voltametry. From the study, electron transfer
mechanisms were proposed. Thermal decomposition studies of some metal
complexes resulted some valuable information regarding the thermal stabilities
of the metal complexes. The fluorescence properties of some metal complexes
have also been investigated. With respect to the significant applications of
Schiff bases and their metal complexes in medicinal field, appropriately termed
as “Medicinal Inorganic Chemistry”; Schiff bases and their metal complexes
have been evaluated for their antibacterial and antifungal activities. Also, some
of the metal complexes have been tested for their DNA cleavage properties on
isolated genomic DNA of various human pathogens.
15
The main purpose of this research work has been to synthesize some new
Schiff bases to utilize as ligands and to study the ligands and their metal
complexes from a structural point of view. These ligands with a variety of
bonding interactions, tautomeric phenomena, potential variety of bonding
modes and hydrogen bonding interactions, were expected to provide
stimulating results. This expectation became fruitful. Metal chelates of Schiff
bases hold exciting possibilities for the future concerning to their wide
applications viz. in designing new catalytic systems, in formulating new
synthetic route, in developing new analytical reagents and in metal based
antimicrobial agents etc., Hopefully, the results of this investigation would
attract increased interest in this field.
Schiff Bases Synthesized in the Present Investigation
The following series of new Schiff bases have been synthesized in the
present research investigation.
1. Synthesis of Schiff bases derived from 8-formyl-7-hydroxy-4
methylcoumarin/5-formyl-6-hydroxycoumarin and 4, 4’-
diaminodiphenyl sulfone (Dapsone) (Figure-I).
2. Synthesis of Schiff base derived from novel macrocyclic Schiff bases
derived from bis-(4-amino-5-mercapto-1,2,4-triazole-3-yl)alkanes and
1, 6- bis(2-formylphenyl)hexane (Figure-II).
3. Synthesis of Schiff bases derived from 4-Aminoantipyrine and 8-
formyl-7-hydroxy-4-methylcoumarin / 5-formyl-6-hydroxy coumarin
(Figure-III). 4. Synthesis of Schiff bases derived from Isatin monohydrazone and P-
Dimethylamino benzaldeyde (Figure -IV).
5. Synthesis of Schiff bases derived from o-substituted thiosemicarbazides
and 8-formyl-7-hydroxy-4-methylcoumarin (Figure -V).
6. Synthesis of Schiff bases derived from Substituted 1,2,4-triazoles
and Isatin (Figure - VI).
N N
SO2
OO
CH3
CH
OH OOH
CH
O
CH3
N N
SO2
O
CH
OH
O O O
CH
OH
Schiff base-I Schiff base-II
n=1, 2, 3 & 4
NO
NN CH3
O
CH3
CH
OOH
CH3
N CH3
N
O N
CH
O O
OH
CH3
Schiff base-I Schiff base-II
(Figure-I)
���������
���������
17
N O
N-N= NCH3
CH3
CH
Schiff baseH
R
R = H, CH3, Cl
NH C N
HN
S
HC
O
O
OH
CH3
�
N O
N NN
N
R
SH
H
R = H,CH3,C2H5,C3H7 �
����������
����������
����������
18
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