Introduction```

Inorganic elements play crucial role in biological and biological

medical processes, and it is evident that many organic
compounds used in medicine do not have a purely organic mode
of action, some are activated or bio transformed by metal ions
metabolism . Many drugs possess modified toxicological and
pharmacological properties in the form of metal complex and
probably Schiff bases are versatile C=N (Imine) containing
compounds possessing broad spectrum of biological activity and
incorporation of metals in form of complexes showed some
degree of antibacterial, antifungal , antitumor and anti-
inflammatory activity.[1] Schiff base are the compound
containing azomethine group (-HC=N-). They are condensation
products of ketones (or) aldehydes (aldehyde and ketones) with
primary amines and were first reported by Hugo Schiff in 1864.
[2] Formation of Schiff base generally takes place under acids or
base catalysis or with heat. The common Schiff base are
crystalline solids, which are feebly basic but at least some form
insoluble salts with strong acids. Schiff base are used as
intermediates for the synthesis of amino acids or as ligands for
Preparation of metal complexes having a series of different
structures. A Schiff base behaves as a Flexi-dentate ligand and
commonly co-ordinates through the O atom of the de -pronated
phenolic group and the N atom of azomethine group.[3] In
Schiff base azomethane nitrogen and other donor atoms like
oxygen play a vital role in co-ordination chemistry. Hence an
attempt is made to study the interaction of reduced Schiff base
with transition of metals of biological interest and to investigate
the co-ordination chemistry of such interactions. In the present
work we described the synthesis and characterization of reduced
Schiff base and its metal complexes.[4] Moreover antibacterial
and analgesic activity of reduced Schiff base metal complexes is
also evaluated and compared with the standards.[5] Aromatic
aldehydes especially with an effective conjugation system, form
stable Schiff bases, where as those aliphatic aldehydes are
unstable and readily polymerize. [6] Schiff base ligands with
aldehydes are formed more readily than with ketone (carbonyl
carbon).Schiff bases have very flexible and different structures.
A wide range of Schiff base compounds and their behavior
studied because these compounds have very flexible and diverse
structure[7]Schiff bases are generally are bi ,tri, or tetra-dentate
chelate ligands and from very stable complexes with metal ions.
Their chemical and physical properties in various field such as
preparative uses, identification, or protection and determination
of aldehyde or ketones, purification of carbonyl and amino
compounds or production of these compounds in complex or
sensitive reactions have studied by various workers [8,9] Schiff
base ligands have significant importance in chemistry ,
especially in the development of Schiff base complexes ,
because Schiff base complexes are potentially capable of
forming stable complexes with metal ions, Many Schiff base
complexes show excellent catalytic activity in various reaction
at high temperature and in the presence of moisture . Over the
past few years, there have been many report on their
applications in homogeneous and heterogeneous catalysis, hence
the need for a review article highlighting the catalytic activity of
Schiff base complexes. Metal complexes [ Co(II),Cu(II) and
Zn(II) ions ] of Schiff base having played a central role in the
development of co-ordination chemistry. Transition metal
complexes have attracted curiosity due to DNA binding and
cleavage properties under physiological conditions. Applications
of metal complexes as chemical nucleases are the focus of
current research .It has been demonstrated that in-organic
complexes as chemical nucleases are the focus of current
research .It has been demonstrated that inorganic complexes can
be used in foot printing studies as sequence specific DNA
binding agents, as diagnostic agents in medicinal applications
.and for genomic research
 Mechanism
The formation of a Schiff base from an aldehydes (or) ketones is
a reversible reaction and generally
takes place under acid (or) base catalysis, or upon heating. The
formation is generally driven to the completion
by separation of the product or removal of water, or both. Many
Schiff bases can be hydrolyzed back to their

aldehydes or ketones and amines by aqueous acid or base. [11]

The dehydration of carbinolamine is also catalyzed by base.
This reaction is somewhat analogous to the
E2 elimination of alkyl halides except that it is not a concerted
reaction. It proceeds in two steps through an
anionic intermediate. The Schiff base formation is really a
sequence of two types of reactions, i.e. addition
followed by elimination
Yet the acid concentration cannot be too high because amines
are basic compounds. If the amine is
protonated and becomes non-nucleophile, equilibrium is pulled
to the left and carbinolamine formation cannot

occur. Therefore, many Schiff bases synthesis are best carried

.out at mild acidic pH

The mechanism of Schiff base formation is another variation on

the theme of nucleophile addition to
the carbonyl group. In this case, the nucleophile is the amine. In
the first part of the mechanism, the amine reacts
with the aldehyde or ketone to give an unstable addition
compound called carbinolamine. The carbinolamine
loses water by either acid or base catalyzed pathways. Since the
carbinolamine is an alcohol, it undergoes acid
catalyzed dehydration.
Iminium salt (R2C=N+R2) at the other extremes are very
rapidly hydrolyzed by water and have to be
prepared under rigorously anhydrous conditions. The facility of
iminium salt hydrolysis has been put to use in a
synthesis of secondary amines from primary amines which
involves conversion into the aldimine (R1CH=NR2)
and then by alkylation in to the iminium salt [R1CH=N+R2 (R3)
X-] followed by hydrolysis to give the secondary
amines (R2NHR3). Because of the involvement of Schiff base
hydrolysis in a number of enzyme mediated
processes, the detailed mechanism of hydrolytic cleavage of
carbon-nitrogen double bonds have been the subject
of close scrutiny both under in vivo and under in vitro
conditions12. Imines hydrolysis is also a key step in the

Sommelet, Stephen, Sonn-MulIer and Gattermann aldehyde

.synthesis

1.1 Biological Importance of Schiff bases

Schiff bases have a large number of synthetic uses in organic
chemistry. Acylation of Schiff bases by
acid anhydrides, acid chlorides and acyl cyanides is initiated by
attack at the nitrogen atom and leads to net
addition of the acylation agent to the carbon-nitrogen double
bond. Reactions of this type have been put to good
use in natural product synthesis.[12] Schiff bases appear to be an
important intermediate in a number of
enzymatic reactions involving interaction of an enzyme with an
amino or a carbonyl group of the substrate. One
of the most important types of catalytic mechanism is the
biochemical process which involves the condensation
of a primary amine in an enzyme usually that of a lysine residue,
with a carbonyl group of the substrate to form
an imine or Schiff base.
Stereo chemical investigation carried out with the aid of
molecular model showed that Schiff base
formed between methylglyoxal and the amino group of the
lysine side chains of proteins can bent back in such a
way towards the N atom of peptide groups that a charge transfer
can occur between these groups and oxygen
atoms of the Schiff bases[13]. In this respect pyridoxal Schiff
bases derived from pyridoxal and amino acids
have been prepared and studied from the biological point of
view.
Several studies have revealed that by condensation of
salicylaldehyde with different heterocyclic
compound and their[14,15] derivative with potent antibacterial
and antifungal activity obtained .

References
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[2].
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N.R., Asain J.Chem,15,1184(2003).
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Indian Chem Soc,80, 138(2003)
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1099(1981).
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Z.H Chohar, P.A Humayun, K.M Khan, J.Enzyme .[15]

.Inhibition and Med Chem, 19,161(2004)

.…Part one Finished

1.1 - SCHIFF BASES

Schiff bases are formed typically by the condensation of
a primary amine and an aldehyde/ketone. The resultant
compound, R1R2C=NR3 is called a Schiff base, where
R1 is an aryl group, R2 is a hydrogen atom and R3 is
either an alkyl or aryl group. However, usually
compounds where R3 is an alkyl or aromatic group are
also regarded as Schiff bases. Schiff bases that contain
aryl substituents are substantially more stable and readily
synthesised, while those which contain alkyl substituents
are relatively unstable. Schiff bases of aliphatic
aldehydes are relatively unstable and readily
polymerisable [1], while those of aromatic aldehydes
having effective conjugation are more stable. In general,
aldehydes react faster than ketones in condensation
reactions, leading to the formation of Schiff bases as the
reaction centre of aldehydes 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
aldehydes [2].
Schiff bases are generally bidentate (1), tridentate (2),
tetradentate (3) or polydentate (4) ligands capable of
forming very stable complexes with transition metals.
They can only act as coordinating ligands if they bear a
functional group, usually the hydroxyl, sufficiently near
the site of condensation in such a way that a five or six
membered ring can be formed when reacting with a
.metal ion

Schiff bases derived from aromatic amines and aromatic

aldehydes have a wide variety of applications in many
fields, eg., biological, inorganic and analytical chemistry
[3, 4]. Applications of many new analytical devices
require the presence of organic reagents as essential
compounds of the measuring system.
Transition metal complexes with Schiff bases have
expanded enormously and embraced wide and diversified
subjects comprising vast areas of organometallic
compounds and various aspects of biocoordination
chemistry [5]. The design and synthesis of symmetrical
Schiff bases derived from the 1:2 step wise condensation
of carbonyl compounds, with alkyl or aryl diamines and
a wide range of aldehyde or ketone functionalities, as
well as their metal(II) complexes have
been of interest due to their preparative accessibility,
structural variability and tunable electronic properties
allowing to carry out systematic reactivity studies based
ancillary ligand modifications. In recent years much
effort has been put in synthesis and characterization of
mono- and bi-nuclear transition metal complexes [6].
Schiff bases are used in optical and electrochemical
sensors, as well as in various chromatographic methods
to enable detection of enhanced selectivity and
sensitivity [7-9]. Among the organic reagents actually
used, Schiff bases possess excellent characteristics,
structural similarities with natural biological substances,
relatively simple preparation procedures and the
synthetic flexibility that enables design of suitable
structural properties [10]. Schiff bases are widely
applicable in analytical determination, using reactions of
condensation of primary amines and carbonyl
compounds in which the azomethine bond is formed
(determination of compounds with an amino or carbonyl
group) using complex forming reactions (determination
of amines, carbonyl compounds and metal ions) or
utilizing the variation in their spectroscopic
characteristics following changes in pH and solvent [11].
Schiff bases play important roles in coordination
chemistry as they easily form stable complexes with
most transition metal ions [12]. In organic synthesis,
Schiff base reactions are useful in making carbon-
.nitrogen bonds

1.2 - BIOLOGICAL IMPORTANCE OF SCHIFF

BASES
Many biologically important Schiff bases have been
reported in the literature possessing antimicrobial,
antibacterial, antifungal, anti-inflammatory,
anticonvulsant, antitumour and anti HIV activities [13-
16]. Another important role of Schiff base structure is in
transamination [17]. Transamination reactions are
catalysed by a class of enzymes called transaminases.
Transaminases are found in mitochondria and cytosal of
eukaryotic cells. Schiff base formation
is also involved in the chemistry of vision, where the
reaction occurs between the aldehyde function of 11-cis-
retinal and amino group of the protein (opsin) [18]. The
biosynthesis of porphyrin, for which glycine is a
precursor, is another important pathway, which involves
the intermediate formation of Schiff base between keto
group of one molecule of δ-aminolevulinic acid and ε-
amino group of lysine residue of an enzyme.
Schiff base ligands may contain a variety of substituents
with different electron-donating or electron-withdrawing
groups and therefore may have interesting chemical
properties. They have attracted particular interest due to
their biological activities [19] eg., acting as radio
pharmaceuticals for cancer targeting [20]. They have also
been used as model systems for biological
macromolecules. Besides the biological activity, solid-
state thermochromism and photochromism are an another
characteristic of these compounds leading to their
application in various areas of materials science such as
the control and measurement of radiation intensity,
display systems and optical memory devices [21].
Schiff bases derived from the salicylaldehydes with two
or more donor atoms are well known as polydentate
ligands, coordinating in deprotonated or neutral forms.
The ability of metal ions to control the oxidation
potentials of organic molecules by complexation has a
significant role in biological electron transfer processes,
molecular electronics and also in catalysis [22]. Schiff
bases are used as corrosion inhibitor e.g. fluorinated
Schiff base derived from 3,4-difluorobenzaldehyde and
.4,4′-benzidine were used as inhibitor in steel
 SCHIFF BASE METAL COMPLEXES - 1.3
Transition metals are known to form Schiff base
complexes and Schiff bases have often been used as
chelating ligands in the field of coordination chemistry.
Their metal complexes
have been of great interest for many years. It is well
known that N, O and S atoms play a key role in the
coordination of metals at the active sites of numerous
metallobiomolecules [23]. Schiff base metal complexes
have been widely studied because they have industrial,
antifungal, antibacterial, anticancer, antiviral and
herbicidal applications [24-26]. They serve as models for
biologically important species and find applications in
biomimetic catalytic reactions. It is known that the
existence of metal ions bonded to biologically active
.compounds may enhance their activities
There are certain metallo-elements without which the
normal functioning of living organism is inconceivable.
Among these metallo-elements so called, ‘metals of life’,
four members form an island. These are Na, Mg, K and
Ca, the transition elements are V, Cr, Mn, Fe, Co, Ni, Cu
and Zn. These elements are present at trace and ultra
trace quantities and play vital roles at the molecular level
in a living system. These transition elements are known
. to form Schiff base complexes
Schiff base metal complexes have been known since the
mid nineteenth century [27] and even before the general
preparation of the Schiff base ligands themselves. Schiff
base metal complexes have occupied a central place in
the development of coordination chemistry after the
work of Jorgensen and Werner [28]. Ettlings isolated a
dark green crystalline product from the reaction of cupric
acetate, salicylaldehyde and aqueous ammonia. Schiff
prepared complexes of metal-salicylaldehyde with
primary amines [29]. Subsequently, Schiff [30] prepared
complexes from the condensates of urea and
salicylaldehyde. Delephine prepared complexes [31] by
reacting metal acetate, salicylaldehyde and a primary
. amine in alcohol and demonstrated a 2:1 stoichiometry
However, there was no comprehensive, systematic study
until the preparative work of Pfeiffer and associates [32].
Pfeiffer and his coworkers [33] reported a series of
complexes derived from Schiff bases of salicylaldehyde
. and its substituted analogues
The study of binuclear and polynuclear complexes of
transition metal ions has received a growing attention in
recent years. It has been an interesting area for chemists,
physicists and biologists, since these complexes form the
basis of several research fields such as bioinorganic
chemistry, magneto chemistry, material science,
catalysis, super conductivity and multi electron redox
chemistry etc., [34, 35]
The transition metal complexes having oxygen and
nitrogen donor Schiff bases possess unusual
configurations and structural labiality and are sensitive to
the molecular environment. 2-hydroxy Schiff base
ligands and their complexes derived from the reaction of
derivatives of salicylaldehyde with amines have been
extensively studied in great details for their various
crystallographic, structural and magnetic features [36-38]
Particularly, a large number of transition metal
complexes of Schiff base ligands derived from the
condensation of salicylaldehyde and 2-hydroxyl-1-
naphthaldehyde with various primary amines became the
topic of contemporary research [39, 40]. These Schiff
base ligands may act as bidentate N,O-, tridentate
N,O,O-, N,O,N-, N,O,S-, tetradentate N,N,O,O-, hexa
dentate N,N,O,O,S,S- donor ligands [41] etc., which can
be designed to yield mononuclear or binuclear
complexes or one-dimensional (1D), two-dimensional
(2D) and three-dimensional (3D) metal-organic frame
works [42]. Although several kinds of metal ions are
found, metallo proteins with transition metal ions are
numerous. The main reason for the preference of
transition metal ions over the other
metal ions is ultimately due to their unique features such
as the flexibility to adopt more than one-coordination
geometries and the ability to exist in multiple oxidation
states. Natural systems utilize one or both of these
.features for their feasible biological transformations
A rational control of the nuclearity of transition metal
complexes is important to design systems with the
desired properties as some of these applications require
the presence of more than one metal centre in the
particular complex. Indeed, binuclear complexes may
have different reactivity than mononuclear counterparts,
thereby enabling transformations inaccessible to single
metal ions [43]. For instance, nucleic acid hydrolysis is
postulated to be facilitated by the cooperative action of
.two metal ions [44]
Schiff base ligands that are able to form binuclear
transition metal complexes are useful to study the
relation between structures and magnetic exchange
interactions [45], and to mimic bimetallic biosites in
various proteins and enzymes [46]. The complexes thus
play an important role in developing the coordination
chemistry related to catalysis, enzymatic reactions,
magnetism and bioinorganic modeling studies [47]. In
this regard, there is much interest in designing
dinucleating ligands and their transition metal
.complexes
Metal ions play an important role in living system both in
growth and in metabolism. The active sites of the
biomolecules [48] are coordination complexes
comprising of one or more metal ions. The potential
relation and those of synthetic coordination complexes
has contributed significantly to the emergence of
interdisciplinary field of bioinorganic chemistry. The
bioinorganic chemistry [49] forms the molecular basis of
all possible interactions between the biological molecules
and metal ions which is inturn applied in the field of
,medicine, biology
environmental sciences, catalysis and technology. So the
:research activities have been grouped as follows
Study of the metal coordination environment in .1
metallo proteins, nucleic acids, carbohydrates,
.membranes [50, 51]
Study of the mechanism of reactions occurring at a .2
.metal center in enzyme [52]
Study of synthetic analog for the active sites in .3
metallo proteins (design, synthesis, structure,
spectroscopy and applications like catalytic reactions and
.metal sequestering from waste water and deposits) [53]
Design and study of metal containing drugs to cure or .4
prevent diseases (36 g) (synthesis and mechanism of
.action)
Removal of metal ions and metal compounds from .5
the living system (detoxification) [54]. In all these fields,
both the metal and the ligands are of important for the
structure, the stability and the process that are regulated
.and catalysed by the metal species
Of all the Schiff base complexes, those derived from
salicylaldimine have been thoroughly studied so far. A
variety of physicochemical investigations on these
complexes provide a clear understanding of their
stereochemical and electronic properties. The advantage
of the salicylaldimine ligand system is the considerable
flexibility of the synthetic procedure, which has resulted
in the preparation of a wide variety of complexes with a
given metal whose properties are often dependent on the
.ligand structure

COPPER - 1.4
Copper is the third most abundant element among the
transition metal ions found to be involved in biological
processes [55]. Copper is a bio-essential element with
truly unique chemical characteristics in its two relevant
oxidation states I and II [56]. According to its position as
the highest homologue of group XII in the periodic table,
copper is a very special element. The metal-ligand
interation in Cu(II) complexes is frequently ionic and
favours the stabilization of the Cu(II) state through the
pronounced Jahn-Teller distortion. Different extent of
axial elongation of the octahedron can produce square-
pyramidal, square bipyramidal or square planar
.geometries
Copper being an essential trace element, is present in
parts per million concentration range in biological
systems. The element functions as a key cofactor in a
diverse array of biological oxidation reduction reactions
[57]. Copper containing proteins (hemocyanin,
tyrosinase, catecol oxidase etc.,) are involved in various
.processes in living systems [58, 59]

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58. E.I. Solomon, U.M. Sundaram and T.E. Machonkin, Chem.
Rev., 96 (1996) 2563.
M. Gonzalez-Alvarez, G. Alzuet, J. Borras, M. Pitie and B. .59
.Meunier. J. Biol. Inorg. Chem., 8 (2003) 644

… Part two finished

1.1: Introduction of Schiff bases

Synthesis of the Schiff-bases were the condensation
reaction product of primary
amines or secondary amine with Aldehydes or ketones to
form the imines which contain
functional group is >CH=N- having double bond. Schiff-
bases will polymerize or
decompose fastly unless, there is at least one of the aryl
group bonded with nitrogen or the
carbon atom of the imines.
Schiff base is a class of organic compounds which are
also known as azomethine,
anilino or imines, have attained significant position in the
subject of Co-ordination
Chemistry due to its various application. When it is
utilized as a ligand in the formation of
metal ion complexes. The Schiff bases were act as a
excellent ligands to form complexes with
various transitional metal ions due to its ability to donate
proton/electron and number of
bonding sides. which guides the different stereo-
chemical structures and also provides the
information related to the kinetic stability and
thermodynamic stabilities of the complexes.
However, mono-dentate Schiff-base ligands were
prepared & these prepared Schiff bases
were used for preparation various types of metal ion
complexes having, bi-dentate, tri-dentate
or tetra-dentate ligands, normally we called as multi-
dentate ligands, which are the great
importance because due to its chelation property. Hence
extra stability of the metal ion
complexes having interesting geometries were observed.
Schiff bases are the special types of organic compounds,
named after the work done
by a German chemist Hugo-Schiff, he will condensed
carbonyl compounds with primary
amines to get azomethine group ( >CH = N- ) as follows:
>C = O + H2N – R > C H= N – R + H2O
The reaction takes place the formation of a
carbinolamine as an intermediate :
>C = O + H2N – R >C – N – R >CH = N – R +
H2O
OH H
Carbinolamine
In the polydentate Schiff base ligands are found to have
along with the main
functional group azomethine, the other potential donor
sites contain various electronegative
atoms such as Oxygen, Nitrogen and Sulphur. It is
observed that, complexes of Schiff- bases
are used to a large extent in various fields such as in
pigment and dye-stuff Industries due to
the variety of coloured transition metal complexesand
also in Polymer industry,
Textile industry, Rubber industry and so on. The Schiff
-base complexes with some
transitional metal ions like cobalt(II) are used as catalysts
for the selective-oxidation reaction
of phenols by dioxygen to quinols or quinines in good
yield. The fluorescent emission
is utilized for the fluorimetric determination of the metal
complexes of Schiff bases such as
Zn(II) & Co(II) metal ion complexes of 2,2'-
dimethylthio-N-salicylidineethylenediamine.
The metal complexes of Schiff bases are also found to
exhibit
luminescence.
The metal ion complexes of Schiff- bases were
extensively studied mainly for its
biological applications for their fungicidal and
insecticidal activity.The Schiff base of
some transitional metal ion complexes play a vital role in
biological systems with many of
them showing oxygen binding capacity. The synthetic
reversible oxygen carrying complexes
are of interest as model compounds in the studying the
mechanism of reversible oxygenation
involved in a complex natural oxygen carrier such as
haemoglobin.
The transition metal complexes of some Schiff bases
which contain sulphur are
reported to exhibit anticancer and antitumor activity.
Similarly, Medicinal properties
have been reported for the Schiff bases prepared from
semi-carbazones and thio-carbazones
The Schiff- bases were prominently used as a analytical.
reagents in analytical
chemistry, since they have excellent ligational property.
The some transitional metal ion complexes of Schiff-
Base are known in 19th century
and even though before the general synthesis of Schiff-
base ligands themselves. The
complexes of Schiff base are found to occupy a main
position in the development of coordination
chemistry after the research work done by Jorgensen and
Werner .
Stallings isolated dark green crystalline product from the
reaction of cupric acetate,
salicylaldehyde and aqueous ammonia. Schiff bases
prepared complexes of metal and
salicylaldehyde with primary amines. Subsequently,
Schiff base complexes were
prepared from the condensate of urea and
salicylaldehyde. Delaine prepared
complexes by reacting metal acetate, salicylaldehyde and
a primary amine in alcohol and
demonstrated a 2:1 stoichiometric. However, it has been
found that, there is no any
comprehensive, systematic study until the preparative
work of Pfeiffer and associates .
Schiff bases are synthesized from the condensation
reaction of a primary amines with
Aldehydes or Ketones. Schiff- bases are important
mediators for the preparation of different
types bio-active molecules. They have detail information
to the different types of biological
activities like anti-bacterial, anti-fungal, anti- cancer and
herbicidal activities.
However, they are used as necessary substances for
preparation of many Schiff- base
ligands, which are used as chiral-auxiliaries in symmetric
preparations. Metal ion complexes
Schiff- bases are also used in oxidation reactions. From
the view of all these reality, we
have concluded that, Schiff bases are significant not only
in medical chemistry, but also in
organic and inorganic synthetic chemistry. Schiff bases
and their metal complexes are
.synthesized in various methods

Being a very best electron-donor group (>CH=N- group), it has

to form various types
of complexes with 3d,4d and 5d series transitional metals ions,
which are called as main
group metal ions. Synthesis of mono, di, tri and tetra dentate
metal ion complexes based on
the growth of ‘multi-component supramolecular’ structure is a
fast developing area of
research. The use of compartmental ligands, suitable for holding
metal ions in close after
to the significant for this aim. In this thesis, mono, di and
tridentate, Schiff-base ligands have
been selected and synthesized with some transition metal ions.
Photo-physical properties of
transition metal ions complexes with Schiff-bases ligands and its
applications were studied.
Various transition metal ion complexes of 3-d series have been
all ready studied and
show luminescent properties. Schiff -bases such as tri-dentate
ligand complexes of
Lnq3(q= 8-hydroxyquinoline) and its corresponding as
luminescent materials in
commercial applications like ‘organic light-emitting devices’.
Schiff base complexes
were studied to be the valuable particles having superior
electron transport capability in twolayer
cell structure. Different studies have been focused on di-valent
transitional metal ion
complexes with macro-cyclic ligands such as mono, di and tri-
dentate Schiff Base ligands. In
this view of its probable relevance as contrast agents for
magnetic resonance imaging,
catalysts in ribose nucleic acid hydrolysis &luminescent stains
for fluoro-immuno and
protein address tag.
However, due to agreeable thirst for fluorescence by rot of the
excited electron shade
with ‘inner-shell d orbital’s’, it was commonly observed that,
systems containing transition
metal ion complexes would not exhibits powerful luminescent
properties. In 2004, the
incorporation of acetylide into metal complexes were
established to destabilize non-radiative
‘d-d’ transitions and to sustain precise structural sincerity, thus
displaying reasonable
luminescence properties. Many such types of compounds were
difficult or even
impossible to prepared by common preparation methods, so they
have been prepared by the
template process or microwave synthesis for long time reaction.
There is no correct definition
of what reaction is called a template type of reaction. Template
processes reactions are those
in which the metal ion, or another center that have been a
definite stereo-chemistry and
electronic state, serves as a model or pattern for forming
appropriate building blocks. The
template effect of the metals are two types these are;
(i) Polymerization reactions are suppressed, since the
concentration of reactants is very
low around the metal ion.
(ii) Multi-step reactions were possible, hence the metal ions
binds the reactants together.
Experimental data indicates that, the product yield of the
template reaction is
sensitive to a number of factors including order of reaction,
addition of reagents, H+ ion
concentration, anion of metal salts, solvent and temperature. On
the basis of this , it has been
postulated that (i) organic intermediates involved in the reaction,
(ii) the product of the
reaction and ligand must be formed before the point, where the
metal salt are added and (iii)
the co-ordination of the organic precursor occur. The methodical
studies of the mechanism
were shown that, the Schiff base formation depends upon the
order of reaction, which the
reactants were mixed. Hence It is concluded that, the
equilibrium is accomplished fastly,
when the metal contents are added lastly. Co-ordination upon
the Schiff base have two
effects;
(i) It would assist to removal of the NH protons and
(ii) It would increase nucleophilic attack on the carbon of the
carbonyl group.
Metal chelates and chelating agents:
A complex compound is formed when a central metal ion (M)
units with a group of
neutral molecules or ions. The later are called ligands (L) which
are capable of functioning as
the donor partner to the central ion. The acceptor, to form co-
ordinate compounds. The
bonding between metal and ligand is called a metal ligand bond
(M-L). The heterocyclic ring
formation, due to the combination of the ligand containing two
or more donor groups with
metal ions as a member, result in the formation of complex or
metal complexes . The process
is known as chelation and the molecule forming a chelate with
the metal ion is known as
chelating agent. The chelates may be viewed from at least three
different angles.
i) Central metal atom
ii) The chelating molecules or ligands
.iii) The nature of bonding between the metal and ligand

i) Central Metal Atom

The properties of the metal chelates are influenced to a large
extent by the nature,
Oxidation state and Co-ordination number of the central metal
atoms . This can be examined
by comparing with Schiff base by different metal atoms with
specific chelating agent. The
structures and properties of the complexes formed by a metal are
influenced by its oxidation
state or oxidation number. They are also influenced by the Co-
ordination number which is the
number of donor or ligand atom directly bonded to the central
metal atoms. This number is
.not fixed and is variable for each metal

ii) Chelating molecules

The molecules, possessing the ability to form chelate rings are
mostly organic in nature
and formed covalent, co-ordinate or both types of linkage
through donor atoms of the Schiff
bases. The Schiff basest must satisfy the following two
conditions to take part in chelation.
a) The molecule must possess two or more functional groups,
the donor atoms are capable
for combining with a metal atom by donating a lone-pair of
electrons. Some are acidic
groups which unite with metal ions by replacement of hydrogen
are – COOH, OH
(Embolic and phenolic), SO3H, = NOH, -SH etc. The
coordinating group also include
O-R, -O-, -NH2, =NH, N, =NOH, -OH (alcoholic), -S- (Thio-
ether), etc. are the
coordinating groups.
b) The molecule must have its functional group, so situated as to
involve in the formation
of a ring with the metal atom as one of the closing members.
These two conditions are necessary, but not always sufficient for
the formation of a
chelate ring. Under some conditions, steric factors occasionally
influence chelation, which is
clearly evident from Cu(II) and Fe(III) chelates with 2, 9-
dimethyl 1, 10, phenanthroline.
The stability of metal complexes are influenced by the following
factors:
1) The size of the chelate ring
2) The number of rings (fused rings in multi-dentate chelating
mol.)
3) The basic strength of the Schiff base.
4) Substitution in the Schiff base, which may modify the basic
strength or the -bonding or
introduce steric effects.
5) The nature of the donor or ligand atoms.
6) Influence of the central metal atom.
1.2 :Classification Of Schiff Base
The Schiff bases have more than two positions through which
covalent or coordinate
linkage can be established with the metal ion. These molecules
which have two three site for
chelation are called bi, tridentate ligands respectively. The Schiff
bases may be classified on
the basis of the type and the functional groups which is present
in the molecules. For
example, the bidentate ligands are divided into three classes:
a) Those containing two acidic groups.
b) Those containing one acidic and one basic groups like –
COOH & NH2.
Schiff bases and their complexes with metals are classified on
the basis of donor
atoms present in the ligands. Thus there are large number of
organic and inorganic ligands
containing donor atoms like O, N, & S, etc.
1.2.1:Metal Chelates of Oxygen Ligands
The Schiff bases which coordinate through the oxygen donor
atoms include
oxyanions, alkantets, dicarboxylates, O-hydroxyl carbonyl
compounds, etc. The
comparatively rare four-member chelate was presumed to be as
M - C = O in the complexes.
Electronic and infrared spectral studies have suggested a five
membered ring
structure for metal complexes of dicardoxylic acids. An Six,
seven or eight membered ring
structure was reported for the higher homologues of
dicarboxylic acids. In the case of -
diketonates, e.g. acetyl acetone, with undergoes Keto-enol
;tautomerism as shown below
A six membered ring structure has reported for natural
.complexes

1.2.2:Metal Chelates of Nitrogen Ligands

Schiff bases of Nitrogen containing ligands include alkyl and
aryl diamines, substituted
1, 10-phenanthroline and 2, 2' bipyridyl derivatives, biguanide,
and their derivatives etc. The
complexes of this type can be divided into two main groups as
(a) alkyl-and aryl-amine metal
complexes (b), aromatic heterocyclic base complexes. The metal
chelates of ethylene diamine
and its derivatives have been extensively studied. The Mn(II)
and Cd(II) complexes of
dicyandiamide have been studied by sahu and Mohapatra.
1.3 : General Information of Schiff Bases
Schiff bases were the first to condensed carbonyl compounds
with amines and these
condensed products were referred to as Schiff bases. These
bases are commonly known as
anils, imines or azomethines have general structure, R.C:N.R',
where R and R' are alkyl
cyclohexyl, aryl or hetero-dyclic radicals who may be variously
substituted. The active
functional group of these bases is the azomethine ( >C=N ) and
its importance has been
revealed by various biological studies. These Schiff bases are
considered as useful
complexing agents, when a suitable functional group like –
hydroxyl, (-OH), amine (-NH2) is
attached in the molecule, sufficiently close to the azomethine
group, so as to form a chelate
ring upon reaction with a metal ion. Because of the relative ease
with the Schiff bases can be
prepared and for their synthetic flexibility, bases with widely
varying substitution can be
obtained by the selection of the appropriate reactants. The size
of the chelate ring can be
changed with respect to the nature and position of the donor
atoms and groups. All these
factors make the bases a good chelating agent and potential
analytical reagent. The complex
forming ability of the Schiff bases with different transition and
non-transitional metal ion
reflected in the appearance of several papers.
Ni (II) chelates of the general formula [Ni (O.C6H4.CH: NR) 2]
are obtained from
salicylaldehyde dimine and its derivatives where R is –H, -OH,
or alkyl group. The Ni (II)
complexes and the analogues Cu (II) complexes have been
shown to be transplanar
Magnetic study has revealed that some of the diamagnetic Ni
(II) chelates develop
paramagnetism in polar organic solvents.
1.4: Uses of Schiff base
Schiff bases are tremendously used in different fields such as
agriculture, industries,
Pharmaceuticals, medicine and so on. Schiff bases are extremely
useful in analytical
methods, such as condensation reaction of amines and aldehyde
or ketones compounds in
which the azomethine linkage is formed. (purpose of
compounds with an amino or carbonyl
group); using complex formation reactions (purpose of amines,
carbonyl compounds with
metal ions); or development in the change of its spectroscopic
purpose of changes in pH of
the solution or solvent (pH of solvent polarity indicators).
However, mainly of Schiff base
compounds are chemically unbalanced and shows a tendency to
take part in diffrent chemical
equilibrium, like ‘tautomeric’ inter conversions, hydrolysis or
formation of ionized class.
Consequently, victorious relevance’s of Schiff bases requires a
vigilant studies of its
characteristics properties. Fluorescent indicators have different
types of functions and
are generally employed in all cases, where colorimetric
indicators have difficult to examine
or required sensitivity.
Metals are play an key role in the biological and biological
medicinal practices. It is
clearly indicates that, the number of organic molecules were
used in medicine, but they do
not have in the form of organic approach of accomplishment
with some are activated or biotransformed
by metal ions metabolism.
The universal structural characteristic of the azomethine groups
with a general
formulae RHC=N-R’ [ R/ R’ = alkyl, aryl, cycle alkyl or
heterocyclic groups], which may be
variously alternatives. Such compounds are also called as anils,
imines or azomethines
groups. Different studies have give details, the occurrence of a
lone pair of electrons in sp2
hybridized orbital of nitrogen atom of the azomethine group,
which may be considerable for
chemical and biological significance. Since the comparatively
open-mindedness of synthesis,
synthetic elasticity and unique property of imines group, Schiff
bases are normally excellent
chelating agents mainly, when a functional group like hydroxyl
or thio , which are present
near to the azomethine group, hence it forms 5 or 6 member ring
with the central metal ion.
Usefulness of Schiff-base compounds in biological, analytical
and industrial application of
their complexes makes additional investigations in this part
.highly beneficial
1.5: Chelating ability of Schiff bases
The chelating capability is enhanced, when nitrogen atom are
nearby in the
neighborhood of one or more donor atom groups. The
azomethine group carrying ligands i.e.,
Schiff bases have achieved an important arrangement and
become ligands of consideration in
co-ordination chemistry, formation of such compounds proceeds
with better formation of the
complex or chelate.
1.5.1: Tetra dentate bis-Schiff bases
The condensation of diamino compound with salicyldehyde to
get Schiff- base
compounds, which possesses such a structural set up that, two
nitrogen and two oxygen
atoms are available for the formation of the bonds . These
chelates are acknowledged as
‘Salen chelates’ and are comparable to the porphyrin structure,
but this can be simply
synthesized . While the tetra-dentate ligands obtained by
condensation of salicyldehyde and
diamino ethane were initially termed as ‘salen chelates’, but one
more term ‘salen type’ is
now engaged to fight the class of (O, N, N, O) tetra-dentate di
Schiff bases. However, the
artificial drawing of Schiff bases may hold stereogenic centers
and other elements of
chirality.
1.5.2 : Structure of Schiff base macro-cyclic compounds
In addition, the well identified nature condensation reaction of
suitable aldehydes or
Ketone groups with primary amine to obtain Schiff base macro-
cyclic compounds have a big
series of formation of supramolecular and co-ordination
compounds. The excellent
capabilities of Schiff bases to balance the metal ions having
different oxidation states and
.improved its exercise with metal complexes

An exciting use of Schiff- bases as an valuable corrosion

inhibitor, which are depends
upon its capability to rapidly form a monolayer on the surface
that can be protected. The
several profitable inhibitors contain aldehydes or amines, but the
majority probably due to the
imines bond of the Schiff bases are function more strongly in
many cases. The major
communication among the inhibitor and the metal surface are
chemisorptions. The
inhibitor molecule should have centers capable to the forming
bonds with the metal surface
by electron transmit. In this way metal ions perform as an
electrophile and the inhibitor acts
as a Lewis bases. Nucleophilic axes of the oxygen and nitrogen
atoms of the shielding
ligands has a free electron pairs, which are passionately
obtainable for allocation. Both of the
atoms of benzene rings, they generate several absorption sites in
the inhibitor , therefore , it
has permit stable monolayer formation. An imines relationship
between the aldehydes
derived from vitamin-A and the protein opposing in the retina of
the eye plays an vital role in
the chemistry of vision and Imines also have additional
biological importance. Vitamins
are also called co-enzymes importance that, they are acts as the
functioning of some enzymes,
which are large proteins that, catalyze chemical adjustment in
cell. For examples, biologically
significant aldehydes are pyridoxal-phosphate, which are the
active in the form of the vitamin
B-6. Vitamin B-6 provides the co-enzyme by forming imines
with an amino acid grouping an
enzyme.
The co-enzyme bind to the enzyme, which is involved in
transamination reaction, the
transfer of the amino group to from one amino acid to another,
which is vital in the
metabolism and the bio-synthesis of amino acids. In the last
step, enzyme-catalyzed
hydrolysis cleaves the imines to pyridoxal and the modified
amino acid.
1.5.3: Schiff Bases Used As Catalysts
The oxidation of organic ligands are an essential and commonly
used reaction in
laboratory level in an organic preparation, hence , hundreds of
different reagents and methods
were accessible for the oxidation of organic ligands. The
selections of solvent, oxidant,
reaction conditions such as temperature, pressure and number of
reaction steps are crucial in
affecting the speed of reaction and the type and quantity of side-
product produced. The Schiff
base transition metal complexes are a family of smart oxidation
catalysts for a variety of
organic substrates because of their cheap, easy to synthesis, their
chemical and thermal
stability. Important oxidation reactions contain the
transformation of alcohols, either the
subsequent carbonyl compounds or carboxylic acids, the
oxidation of sulfides to sulfoxides,
alkenes to epoxides, diols and the activation of hydrocarbons.
Aromatic schiff bases or its metal ion complexes catalyze
reactions on oxygenation
hydrolyzed, electro-reduction and decomposition. Four co-
ordinated Cobalt (II)
Schiff- base complexes illustrate catalytic properties in
oxygenation of alkenes. Some copper
complexes prepared from amino acid enhance hydrolysis rate
more than simple Cu (II) ion.
Synthetic Fe (II) Schiff- base complex shows catalytic
properties towards electro-reduction of
oxygen. Some transitional metal ion complexes of a polymer
attached with Schiff-bases
proves catalytic property on decomposition of hydrogen
peroxide and oxidation of ascorbic
acid. Cyanohydrins cobaltite complexes have the catalytic
applications.
The natural oil and gas constituents contain a large amount of
hydrocarbons. The
Functionalization of hydro-carbons has been familiar as a type
research policy for the
development of economical and to admit global carbon
management. Definitely one of the
most vital Functionalization is selective oxidation. It is already
known to oxidize aliphatic or
cycloaliphatic compounds in the liquid phase using oxygen or
hydrogen peroxide to
analogous alcohols and/or ketones. The chemical inertness of
hydrocarbon makes the
activation of carbon-hydrogen bonds actually difficult, usually
requiring extreme conditions,
such as high temperature and pressure. The selective oxidation
of cyclo-hexane to cyclohexanone
or cyclo-hexanol is of great industrial importance. Over one
billion tones of
cyclo-hexanol and cyclo-hexanone are produced each year
worldwide, which are mostly used
in the manufacture of the polymers Nylon-6 and Nylon-66. In
the industrial process the
cyclo-hexane is first oxidized to cyclo-hexanol and cyclo-
hexanone using cobalt based
homogeneous catalyst (4% conversion and 70- 80 % selectivity
towards cyclo-hexanol) and
from the products, the adipic acid or caprolactone is obtained .
High temperature and pressure
(423–433 K and 0.9 MPa) are required to form cyclo-hexanol
and cyclo-hexanone. The
subsequent oxidation to adipic acid uses nitric acid as oxidant
which is a very unfriendly
reagent. As early as 1876, Fenton has found that iron(II) salts in
an acidic aqueous solution
using hydrogen peroxide as oxidant is capable of oxidizing
alkanes. Many mechanisms have
been proposed for this reaction, mostly those involving.
Co2+, Fe3+ and Ru3+ complexes of Schiff- bases derivatives
formed form
salicyldehyde were used in oxidation of cyclo-hexane into
cyclo-hexanol and cyclo-hexanone
in presence of hydrogen peroxide. The majority of the catalysts
are Fe3+ complexes are
abnormal. In general, the Co2+ complexes are extremely active
for Alkane oxidation reactions
. Chromium-salen complexes are familiar for catalysts, which
are used for equally forms
in heterogeneous as well as homogeneous catalyst. Bi-
nucleating complexes of Fe2+, Co2+,
Ni2+ and Zn2+metal ions with Schiff bases of neutral
bis(iminopyridyl)-benzene and monoanionic
bis- (imino-pyridyl)phenolate work as catalysts in the
oligomerisation of ethylene.
New Mn2+ and Mn3+ complexes of substituted “N,N’-
bis(salicylidine)-1,2-diimino- 2-
methylene” show to be able models for peroxidase action. Novel
Cu2+ complexes of
‘indoxyl-thiosemi-carbazone’ proves that, one pair of well
different reduction peaks at
different potential in the forward scan, which characterized the
reduction of Cu2+to Cu+ by
one electron process and later oxidation of Cu+. The irreversible
character of the Cu2+to Cu+
is due to intrinsic reducing affinity of thio-semicarbazone
compounds with Ru3+ and Co2+
complexes. A broad series of Co2+ complexes are known to
bind dioxygen atoms with more
or less reversibly. thus, they are frequently studied as a
representation ligands for natural
oxygen carrier and for their use in O2 storage, as well as in
organic preparations due to their
.catalytic properties under malleable conditions

… Part three finished

The Reaction of Salicylaldehyde and

Aniline

Introduction
Aldehydes and ketones show a high degree of
reactivity with respect to nucleophilic attack of the
carbonyl carbon. Ammonia and its derivatives such
as primary amines, hydrazine (N2H4) or
phenylhydrazines (C6H5NHNH2) all react by
initially attacking the carbonyl carbon, followed by
hydrogen transfers to give an amine where the
nitrogen is bonded to a carbon that also contains a
hydroxyl group. Under acidic conditions, the
hydroxyl group is protonated, followed by loss of
water
.to give the conjugate acid of the observed product

Hydrogen ion transfer then gives the Schiff base

product. The condensation step to give water is
acid
catalyzed and is the rate-determining step of the
sequence.
All of the steps of the above sequence are
reversible. In principle, the reaction of water with
the Schiff
base will give back the aldehyde or ketone and the
amine from which it was formed. However, here,
we are using aromatic reagents, which form
products that are more stable than analogous
alkylcontaining
reagents. Ketones do not react as readily as do
.aldehydes

… Part four finished

REVIEW OF LITERATURE
Hasty et al., (1977) synthesized copper(II), nickel(II) and
cobalt(II) complexes having an imino benzene moiety
bridging between the two metal ions [78]. The ligand (I) was
obtained by the condensation of salicylaldehyde with m- or
p-phenylenediamine. The copper and nickel complexes
showed antiferromagnetic interaction and cobalt complex
.showed weak antiferromagnetic exchange interactions

Condensation of 2,2′,6,6′-tetraaminobiphenyl with

salicylaldehyde gives a binucleating ligand (II) which was
used to prepare Cu2(sal-tabp), Ni2(sal-tabp).H2O and
.Co2(sal-tabp).½ H2O

Karaböcek et al., (1997) synthesised and characterised

mono- and di- nuclear copper(II) complexes (III) with a
tetradentate Schiff base, 4′,5′-bis(salicylideneimino)benzo-
15-crown-5 [79]. This ligating system provides an additional
active site besides conferring on the copper(II)
ion in a square planar N2O2 environment which not only
mimics the active site in galactose oxidase but also has a role
.in molecular magnetism

Kanadaswamy et al., (1998) synthesised and

studied remote donor set of complexes (IV)
derived from methylene bridged bis
(tridentate) ligands with the aim to study the
influence of remote donor set of ligands on
complex properties [80]. The EPR spectra is
similar to mononuclear Cu(II) complex with
nuclear spin 3/2. Variable temperature
magnetic susceptibility measurements show
no exchange interation between Cu (II)
.centers

REFERENCES
78. E.F. Hasty, Lon J. Wilson and David N. Hedrickson, Inorg.
Chem., 17 (1978) 1835.
79. S. Karaböcek and N. Karaböcek, Polyhedron, 16 (1997)
1771.
P. Kamatchi and M. Kandaswamy, Polyhedron, 17 (1998) .80
.1397