A STUDY ON TERNARY COMPLEXES OF SOME TRANSITION

AND INNER TRANSITION METAL IONS WITH BIOLOGICALLY

HETEROCYCLIC THIOHDRAZONES

INTRODUCTION
Heterocyclic Mannich Bases
Mannich base is the condensation product of a compound containing at least
one active hydrogen atom, HCHO and ammonia or a primary or secondary
amine. In this research, since the Mannich bases have been synthesized from
benzimidazole, its derivatives and coumarin derivatives (heterocyclic
compounds), therefore the reported Mannich bases are heterocyclic Mannich
bases. The main feature of the reaction is the replacement of the active
hydrogen atom by an aminomethyl or substituted aminomethyl group.

Mechanism of Formation of Mannich Bases

Liebermann and Wagner proposed that the Mannich reaction is due to the
addition of a methyleneammonia cation or a protonated dialkyl amono
ethanol to a carbanian. The addition of amine to formaldehyde has been
considered as the first step of the reaction.
1

O
||

CH2 = N+R2 + - CH C -

- CH - C -

||

O
CH2
NR2

2-Amino benzothiazole Mannich bases prepared by Jacques and co-workers

showed interesting analgesic activity in mice. Mannich bases derived from 5(p) - chlorophenyl 1, 3, 4 oxadiazol -2- thione have been found to exhibit
remarkable fungicidal activity. The Mannich bases of 7- hydroxyl coumarin
derivatives synthesized with aliphatic, heterocyclic amines and amino acids
have been found to have antibacterial activity. A number of Mannich bases
prepared from benzimidazole derivatives showed interesting antimicrobial
activity against S. Aureus, b. Megaterium, bacillus Cereus and Escherichia
Coli.

REVIEW OF LITERATURE

The infrared spectrum of a compound is a fingerprint of the compound.

Although the infrared spectra is characteristic of the entire molecule, certain
groups of atoms give rise to bands at or near the same frequency regardless of
the structure of the rest of the molecule. It is the persistence of these
characteristic bands that permits the chemist to obtain useful structural
information by simple inspection and reference to generalized charts of
characteristic group frequencies.

The infrared spectral studies have gained an unexpected momentum in the

field of coordination chemistry because of their varied uses, such as:
(1) In distinguishing of the nature of various functional moieties present in a
ligand as well as in its metal compounds;
(2) In ascertaining the mode of coordination of the donor atoms with metal;
(3) In providing an idea of a multiple bonding;
(4) In revealing isomerism;
(5) In ascertaining the state of a ligand-whether free or bound, and the degree
of molecular symmetry in a complex.
3

NOTEWORTHY CONTRIBUTIONS

With the advent of ligand field theory our understanding of the electronic
structure of transition metal complexes has rapidly gained momentum. The
electronic spectral studies have been proved to be of great utility since long in
explaining to some extent, the anomalies observed in magnetic moment
values of metal complexes. Various physico-chemical observations such as
stereo-chemistry, magnetism and spectroscopic behaviour of variety of
systems have been satisfactorily interpreted by recent bonding theories.

The magnetic measurements are of much utility in detecting the nature of

bond and deciding the stereochemistry and oxidation state in the complexes.
Substances, in which there are no interactions between adjacent atomic
dipoles, are said to be magnetically dilute. Two types of magnetic behaviour
are found in magnetically dilute substances. In diamagnetic substances X is
negative; in paramagnetic substances it is positive. Diamagnetism arises from
the motions of electrons which are treated as charged particles in the applied
magnetic field while paramagnetism arises from the angular momentum of

ions. The angular momentum may be orbital or spin in origin. Diamagnetism

is independent of temperature.

Layer (2011) reviewed the preparation and properties of Schiff

Their chelating

bases.

characteristics were described in a monograph by Dwyer

and Mellor. Holm and coworkers published an excellent review of Schiff

bases on the metal complexes. Applications of Schiff bases in inorganic
analysis have been described by Jungeis et al. Researches are on progress
over bi tricentered (polymetallic) Schiff base complexes.
Dayagi and Degani (2014) reviewed
synthesis. It was

shown

dithiocarbazide

possess

antineoplastic

activity

that

the procedures

copper

antitumor

and

of Schiff base

palladium chelates of

activity. In recent

past some

in the chelates of platinum group metals and

some of the 3d-transition metals with the Schiff bases derived from 5-methyl
dithiocarbazate,

purine,

6-mercaptopurine and thioguanine have been

reported.

Dave and Mohan Kumar (2013) have studied the Ni(II) and Cu(II)
complexes with quadridentate

Schiff

bases

by condensing

aliphatic

diamines and dihydroxy acetophenone, dihydroxy benzophenone.

RESEARCH METHODOLOGY

The study, being and empirical, will be conducted under two phases. The
first, being the descriptive part of the study. For this part of the study,
secondary information would be obtained from current literature of neural
network, research journals and business new-papers. The other researches
will also be utilized for this purpose. The primary data would be obtained
with the help of open-ended questionnaires, conducting testing &
experiments, different models and discussions with the experts. Thus, with
the help of primary and secondary data, the study would be conducted and
inferences would be drawn to submit useful recommendations.

EXPECTED OUTCOMES OF THE STUDY

The equilibrium or instability constant is the main characteristic of the

complex in solution. Its reciprocal is known as stability constant. Successive
or stepwise formation is of great importance in chemical analysis, solvent
extraction, ion exchange, analytic al separation process and the chelate
formation in various biological systems. The outcomes of the study will be as
follows:
Medicinal Utility: Bases are well known to possess pronounced
biological

activities. Anils

salicylaldehyde

and

obtained

aromatic

by

amines,

the

condensation

o-aminophenol

of
and

polymethylene diamines are found as useful bactericidal and fungicidal

agents, Anticancer Schiff Bases have been prepared by condensing
aniline with some substituted benzaldehydes. Schiff base mustards have
also been subjected to clinical trials. Isoxazoly1 Schiff bases have been
synthesised as possible antibacterial and antifungal agents.
Characterization of the above compounds by elemental analysis and IR
spectra
7

 Evaluation of the antibacterial activity of some of the newly

syntheissed mixed organic complex
Information of the nature of bonding involved in the isolated
complexes by IR and electronic/reflectance spectral studies

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