CHAPTER ONE

1.0 Background of Study

Schiff bases are compounds with a functional group that possess a carbon-nitrogen double bond

with the nitrogen atom connected to an aryl or alkyl group, not with hydrogen. In general sense

schiff bases, could be represented as the general formula R 1R2C=NR3, where R is an organic side

chain. Some of them are restricted to the secondary aldimines (like azomethines as the carbon is

attached with a hydrogen atom) with the general formula RCH=NR'. Carbon-nitrogen double

bond provides a significant contribution in various progresses of chemical sciences. Schiff-base

compounds have been potentially used as fine chemicals and medical substrates. Number of

methods are been applied for synthesis of schiff base. In traditional method of synthesis also

known as organic synthesis, which commonly involve the removal of solvents from the reaction

mixture or liquid extraction especially in the case of aprotic dipolar solvent with high boiling

point, or product isolation through liquid-liquid extraction (Muzammil et al., 2015)

Microwave methods have been popularly used in schiff base synthesis by organic synthesis as it

has several benefits like better atom economy, environmental friendly, less hazardous, etc. In

general mechanism of synthesizing schiff base, an aromatic amine reacts with a carbonyl

compound by nucleophilic addition. This forms a hemiaminal, followed by a dehydration to

produce imines. Schiff bases obtained from aromatic aldehydes and aromatic amines have shown

number of applications in many fields including pharmaceutical, life sciences and chemical

science including inorganic and analytical chemistry (Bader, 2010)

Schiff bases are introduced to coordination as well to be a segment and starting materials for the

synthesis of other chemical compounds or techniques. They are readily synthesized in some
simple routes which gives the compounds their significant advantages of the applications. The

azomethine group in all Schiff bases mainly dominates and influences the properties of the Schiff

bases as the most sites in the Schiff base body. The coordination capability of Schiff bases give

them the advantages to interact with metals. In this aspect, the Schiff base considered as

bidentate ligands. The use of modern methods and tools makes the characterization of Schiff

bases easier to carryout, such methods includes elemental analysis, infrared and other physical

methods when needed. Heating aldehyde with primary amine in appropriate solvents, or even

using microwave techniques will produce the corresponding Schiff base. The process of

coordination could be conjugated to the uptake techniques (Abdussalam et al., 2014). Most of

the transitional metal ions play a role in these reactions, because of their charge, size, electronic

structure and ability to form coordinate molecules. Schiff bases which have been synthesized can

be introduced to coordination reaction, specially, if they have either nitrogen or oxygen or sulfur

atom or any unshared lone pair of electrons on atoms adjacent the azomethine group in order to

form stable chelates with five or six membered rings.

The chemistry of Schiff base compounds has undergone extensive studies and they have shown

to have different applications as coordinating ligands, as catalysts, in electrochemistry, and

medicinal values. Schiff base compounds possess antimicrobial and anti-inflammatory activity. It

has been discovered that the biological activity of some Schiff base ligands became enhanced

upon chelation with metal ions. In some cases, however, the free ligands do possess higher

activity than the corresponding metal complexes, an indication that activity does not depend

solely on the presence of metal ions but rather a unpredicted effect of many factors. Many Schiff

base metal complexes have been prepared and screened for their antimicrobial activity (Sobola et

al., 2014).
The complexes of copper with Schiff bases have wide applications in food industry, dye

industry, analytical chemistry, catalysis, fungicidal, agrochemical, anti-inflammable activity,

antiradical activities and biological activities. Schiff-base complexes are considered to be among

the most important stereo chemical models in main group and transition metal coordination

chemistry due to the ease in their preparation and structural variety (Gemi et al., 2004). Copper

(II) complexes show distorted octahedral and tetrahedral symmetries due to d 9 configuration

(JahnTeller effect). The distortion is usually seen as axial elongation consistent with the lability

and geometric flexibility of the complex. Therefore, typical Cu (II) complexes have square

planar or square pyramidal geometries with weakly associated ligands in the axial position (s),

but some copper (II) complexes possess trigonal bipyramidal geometry. The fundamental role of

copper and the recognition of its complexes as important bioactive compounds in vitro and in

vivo enhance the interest in these agents as potential drugs for therapeutic intervention in various

diseases (Keypour et al., 2009).

Fe (II) complexes have been of interest due to their preparative accessibility, structural

variability and tuneable electronic properties allowing to carry out systematic reactivity studies

based on ancillary ligand modifications, and to mimic bimetallic biosites in various proteins and

enzymes. Fe (II) complexes thus play an important role in developing the coordination

chemistry, catalysis, and enzymatic reactions, magnetism and bioinorganic modelling studies etc.

In this regard, there is much current interest in designing binucleating ligands and their transition

metal complexes (Babu et al., 2017).

1.1 Problem Statement

Schiff base compounds have been synthesized from aniline and p-nitrobenzaldehyde and

characterized for their antimicrobial activities; the results have shown that the Schiff bases have

moderate/lower antimicrobial activities as compared to their complexes. Most of the complexes

showed higher activity than the free ligands of Schiff bases hence, there’s a need to synthesize

metal complexes of Schiff bases with novel characteristics.

1.2 Justification Of Study

Numerous researches have shown that Schiff base compounds derived from carbonyl and amino

groups and their derivatives possess antimicrobial and anti-inflammatory activity. It has been

discovered that the biological activity of some Schiff base ligands became enhanced upon

chelation with metal ions. This research will put some of the synthesizing substrates of the Schiff

base (aniline and p-nitrobenzaldhyde) into consideration, investigating also the enhanced

antimicrobial activities of Cu (ii) and Fe (ii) chelated Schiff base compounds.

1.3 Significance of Study

The study is beneficial as it will provide a new way for the synthesis of Schiff bases and also

metal chelated Schiff base compounds of novel activities which could aid inhibiting or

counteracting the pathogenic action of microbes.

1.4 Scope and Limitation of Study

The research on the synthesis of metal complexes of Schiff bases has covered several methods

such as; classical method, water based method, grindstone method, microwave irradiation

method and ultrasonic method. This research will focus on the water based method of synthesis
of Schiff base from aniline and p-nitrobenzaldehyde and chelating them with Cu (ii) and Fe (ii)

ions.

Hence, this research is limited by time, resources and availability of samples and reagents.

1.5 Aim of the Study

The primary focus of this research is to prepare, characterize and to determine the antimicrobial

activities of metal complexes of Schiff base compounds from aniline and p-nitrobenzaldehyde

using Cu (ii) and Fe (ii) as the chelation ions.

1.6 Objectives of the Study

To achieve the above aims, the following objectives are considered;

i. Synthesizing Schiff base from aniline and p-nitrobenzaldehydes as the basic substrate

ii. Chelating the Schiff base with Cu (ii) and Fe (ii) ions to form metal complexes of the

Schiff base.

iii. Characterizing the prepared metal complexes of Schiff base compounds using some

modern methods such as elemental analysis, FTIR spectroscopy e.t.c.

iv. Carrying out determination on the antimicrobial activities of the prepared metal

complexes of the Schiff base

v. Comparing the antimicrobial activities of the synthesized metal complexes of the Schiff

based to others.
 CHAPTER TWO

2.0 Schiff Bases

Schiff bases are stable compounds containing the carbon-nitrogen double bond (-HC=N-), they

are also called imines. (Imines are present in various naturally derived compounds;

ancistrocladinine and chitosan-derived Schiff base (Bringmann et al., 2004, Guo et al., 2007).

The presence of imine group in these compounds has contributed to their activities.

Figure 1: General representation of Schiff base

The stability of Schiff base compounds are enhanced due to the presence of aryl group which

leads to conjugation in the compound. Schiff bases exhibit delocalized π-electron system which

makes them to have large non-linear polarizabilities, this is usually enhanced by the presence of

donor or acceptor groups. Schiff bases are among the most general nitrogen coordinating ligands,

because the basicity of the sp2 hybridized nitrogen lone pair of the imine nitrogen (although

lower than that of amines sp3 hybrdization) is well suited to form complexes with metal ions.

Schiff bases play important roles in Coordination Chemistry as they easily form stable

complexes with most transition metal ions (Atmaram and Kiran, 2011). The majority of the

ligand systems employed in model studies are derived from Schiff bases (Bailey et al., 1986).

Schiff bases possess structural similarities with naturally occuring biological substances. This
enhances their use in elucidating the mechanism of reaction processes in biological systems such

as transamination and racemination reactions. The relatively simple preparation procedures and

synthetic flexibility which facilitates the introduction of tailor made structural properties allows

their use as ligands for preparation of libraries (Patai, 1970).

2.1 Synthesis of Schiff Bases

Schiff bases are synthesized by condensation reactions between aldehydes and amines. The first

preparation was reported in the 19th century by Hugo Schiff (Schiff, 1864). The synthesis of

Schiff bases is a reversible addition-elimination reaction; hence water elimination is crucial for

product formation. The crude product can be purified by recrystallization or column

chromatography on alumina. Condensation reaction can be achieved using different reaction

methods which utilize either an aldehyde or ketone.

2.2 Synthesis of Schiff Base from Aldehydes and Ketones

The first step of the mechanism generates a carbocation. This reacts with the lone pair of

electrons on the nitrogen in the amine. The unstable product of this step is stabilized by the loss

of an equivalent of water from the molecule, to form a Schiff base. Actually another name for an

imines functional group, in biochemistry a Schiff base is formed by the condensation of an amine

group with the carbonyl group of an aldehyde or ketone. Since the nitrogen of the resulting bond

has basic character (indicated by the lone pair shown explicitly on the nitrogen atom in it can

take up a proton to form the conjugate acid of the Schiff base, or the protonated Schiff base. The

formation of a Schiff base and its functionality are important in the mechanism of a number of

enzymes, including that of aldolase and those, like aminotransferases, using pyridoxal phosphate

as a cofactor (Kumar, et al.,2017)

2.3 Methods of Synthesizing Schiff Bases

The various methods of synthesizing Schiff bases include;

 Classical method

 Water based method

 Grindstone method

 Microwave irradiation method

 Ultrasonic method

2.3.1 Classical method

The synthetic method reported by Hugo Schiff in 1864 is termed the classical method and is still

in use today. This method involves the condensation of a carbonyl compound with an amine in

refluxing condition using organic solvents such as ethanol. The problem of water elimination led

to the use of dehydrating agents. The presence of dehydrating agents to remove water produced

normally favours the formation of SBs. An in-situ method for water elimination using

dehydrating solvents such as tetramethyl orthosilicate or trimethyl orthoformate was developed

in the early 1990’s. However, this method depends on the use of highly electrophilic carbonyl

compounds and strongly nucleophilic amines. Lewis acids such as ZnCl2, MgSO4, NaHCO3,

H2SO4 have also been shown to activate the carbonyl group, catalyse the nucleophilic attack by

amines and dehydrate the system (Chakraborti et al., 2004).

2.3.2 Water Based Method

Water based method involves the use of water as solvent. The reactants are usually water soluble

and are allowed to stir at room temperature before leaving to stand for 48-72 h. The product

obtained is re-crystallized from water. Arshi et al. (2009) reported the synthesis of Schiff bases

from 3-chloro-4-floro aniline and substituted benzaldehyde using water as solvent.

Water being an abundantly available cheap solvent for reactions is environmentally friendly and

encouraged for a green chemistry synthesis. The products are easily isolable, making reactants

easier to handle. However, the method has limited application as most organic compounds are

insoluble in water while the Schiff bases can also undergo hydrolysis in water.

2.3.3 Grindstone Method

Grindstone method of synthesis is a solvent-free reaction. Solvent free reaction used in the

synthesis of imines, Aldol and Michael reactions are fast becoming the best synthetic method

(Tanaka, 2003). The method involves grinding the reactants using a porcelin mortar and pestle

until the mixture turns pasty. The formation of Schiff base occurs on standing over a period that

ranges from several minutes to days. The crude product is re-crystallized from appropriate

solvents such as ethanol. The method has been utilized for the synthesis of bis-imine Schiff base

using diamine and two equivalent of aldehyde. This method is environmentally friendly, high

yield but conversion to product reaction time can be long. However, this method cannot be used

for reactants that are both liquid.

2.3.4 Microwave Irradiation Method

Microwave synthesis of Schiff bases have been performed using microwave irradiation. The

approach uses very little solvent and can also be solvent free when using liquid reactants. The

microwave-assisted condensation is usually carried out in a microwave for short reaction time

usually minutes. Several research groups have reported synthesis of Schiff bases using

microwave irradiation to be fast and efficient (Yang et al., 2002).

Environmetal restrictions on emissions, non-polluting and atom-efficient technologies have

increased interest in such synthetic techniques. Furthermore, there are several advantages of

performing synthesis using microwave irradiation, some of which include: increased safety, short

reaction time, economic advantage due to absence or very little solvent. In addition, solvent free

microwave processes are also clean and efficient.

2.3.5 Ultrasonic Irradiation

Method Ultrasound irradiation has been considered as a clean and useful method in the synthesis

of organic compounds. Many homogeneous and heterogeneous reactions can be conducted

smoothly by sonication to improve yield with increased selectivity. Ultrasonic irradiation

involves the use of ultrasonic processor equipped with long probe, which is immersed directly in

the reaction mixture. The synthesis of Schiff base derivatives containing naphthalene analogues

by the reaction of 2,2-[naphthalene-2,7-diylbis(oxy)]diacetohydrazide with different substituted

aryl/hetero aromatic aldehydes using ultrasonic method have been reported (Venkatesan et al.,

2011).

In comparison with other methods, this technique is more convenient and easily controllable. A

large number of organic reactions can be carried out under milder conditions in shorter reaction
time providing higher yield under ultrasound irradiation. The disadvantage is that expertise is

required and the instrument is expensive.

2.4 Schiff Base Ligands

The presence of a lone pair of electrons in a sp2 hybridized orbital of the nitrogen atom of the

azomethines group is of considerable chemical importance and impart excellent chelating ability

especially when used in combination with one or more donor atoms close to the azomethines

group. This chelating ability of the Schiff bases combined with the ease of preparation and

flexibility in varying the chemical environment about the C=N group makes it an interesting

ligand in coordination chemistry (Kumar, et al., 2017). When an aldehyde is a salicylaldehyde

derivative and the amine is a diamine derivative, the condensation produces interesting N 2 O2

Schiff base compounds.

2.5 The Chemistry of Schiff’s Base Ligands

Chelating ligands in the field of Coordination Chemistry and their Metal Complexes are of great

interest since many years. It is well known that N, S and O atoms play a key role in the

coordination of metals at the active sites of numerous metallobiomolecules. Chelating ligands

containing O, N and S donor atoms show broad biological activity and are of special interest

because of the variety of ways in which they are bonded to metal ions (Pier, 2004). The

condensation of an aldehyde or ketone with primary amine leads to the formation of an imine

called Schiff’s base.

Figure 3: Formation of Schiff’s base from carbonyl compounds in acid catalyzed dehydration

The presence of a dehydrating agent normally favours the formation of Schiff bases. Though the

Schiff’s bases are stable solids, care should be taken in the purification steps as it undergoes

degradation. Chromatographic purification of Schiff’s bases on silica gel is not recommended as

they undergo hydrolysis (Minna, 2007). The common structural feature of these compounds is

the azomethine group with a general formula RHC=N-R’, where R and R’ are alkyl, aryl,

cycloalkyl or heterocyclic groups which may be variously substituted. Presence of a lone pair of

electrons in a sp2 hybridized orbital of nitrogen atom of the azomethine group is of considerable

chemical importance and impart excellent chelating ability especially when used in combination

with one or more donor atoms close to the azomethine group. This chelating ability of the Schiff

bases combined with the ease of preparation and flexibility in varying the chemical environment

about the C=N group makes it an interesting ligand in coordination chemistry (Keypour et al.,

2002)

2.6 Schiff Base Transition Metal Complex and its Activity

Cozzi et al, (2004) in his review has outlined five synthetic routes that are commonly employed

for the preparation of Schiff base metal complexes. The first route involves the use of metal

alkoxides (M (OR) n). Alkoxides of early transition metals (M = Ti, Zr), are commercially

available and easy to handle. The use of other alkoxides derivatives is not easy, particularly in
the case of highly moisture-sensitive derivatives of lanthanides. Metal amides M (NMe2)4 (M =

Ti, Zr) are also employed as the precursors in the preparation of Schiff base metal complexes in

the second route. The reaction occurs via the elimination of the acidic phenolic proton of the

Schiff bases through the formation of volatile NHMe2. Other synthetic routes include treatment

of metal alkyl complexes with Schiff bases (Route 3) or treatment of the Schiff base with the

corresponding metal acetate under reflux conditions (Route 4). The synthetic scheme presented

in the fifth route which is quite effective in obtaining salen-type metal complexes consists of a

two-step reaction involving the deprotonation of the Schiff bases followed by reaction with metal

halides.

2.7 Methods of Characterizing Schiff Bases and their Metal Complexes

Several spectroscopic methods have been used in the analysis of Schiff bases and their metal

complexes. These include infrared (IR), nuclear magnetic resonance (NMR) and electronic

absorption spectroscopy. The thermal analysis methods include thermogravimetric analysis

(TGA) and differential scanning calorimetry (DSC). Magnetic moment measurements have also

been used in assigning geometries to Schiff base metal complexes. All these elucidate different

aspects of the structure.

2.7.1 Elemental Analysis

Novel Schiff’s base Ligands and their complexes are analyzed micro analytically for carbon (C),

hydrogen (H), Sulfur(S) and nitrogen (N) contents to find out their empirical composition. That

means Elemental analysis of a compound enables one to determine the empirical formula of the

compound. The empirical formula is the formula for a compound that contains the smallest set of

integer ratios for the elements in the compound that gives the correct elemental composition by
mass. So physical characteristics and elemental analysis of C, H and N of the compounds are

considered to determine the composition of complexes and the novel ligand. The results of C, H

and N percentage are in accordance with the composition suggested for the most complexes

(Mohammed, 2014).

2.7.2 Infrared Spectroscopy

Infrared spectroscopy deals with the interaction of infrared radiation with matter. It is used to

measure the vibrational frequencies of bonds in a molecule by scanning over a range of

frequencies. Since each bond has a characteristic frequency, any frequency which matches the

characteristic frequency of a bond will absorb infrared radiation. The IR spectrometer can

therefore be used to detect functional groups and provide information about the type of bonds

present. The kind of bond a compound has can be determined by the wavelength of light that are

absorbed by a particular compound. Vibrations can either involve a change in bond length

(stretching) or bond angle (bending). The frequency of bond vibration is affected by the masses

of the atoms in the bond and the strength of the bond, the lower the mass, the higher the vibration

frequency.

2.7.3 1H-NMR spectroscopy

Nuclear magnetic resonance (NMR) spectroscopy is the study of molecular structure through the

interaction of an oscillating radio-frequency electromagnetic field with a collection of nuclei

immersed in an external magnetic field. Nuclear magnetic resonance (NMR) spectroscopy helps

to identify the carbon-hydrogen framework of an organic compound. The number of signals in a

1H NMR spectrum provides information on the kind of protons a molecule contain and the

position of the signal suggests the type of protons present. These protons can be shielded or
deshielded. A shielded proton requires high applied field strength and a deshielded proton

requires a lower applied field strength at which absorption occurs. Shielding shifts the absorption

upfield, and deshielding shifts the absorption downfield. The presence of substiuent groups

affects the field strength around the protons. Electron withdrawing substituents lowers the

electron density in the vicinity of the proton and thus causes deshielding from the magnetic field

while electron donating substituents increases the electron density in the vicinity of the proton

which results in shielding from the magnetic field. The signal for these protons therefore occurs

at a lower magnetic field (high δ) than the signal of the more shielded protons (low δ) which

occurs at a higher magnetic field. The proton NMR spectrum of ligand derived from 4-

aminoantipyrine and 3- salicylideneacetylacetone showed the following signals: C6H5 as a

multiplet at 6.9- 7.5 δ and azomethine proton at 9.8 δ. The peak at 13.4 δ was attributed to the

intramolecular bonded phenolic OH group present in salicylideneacetylacetone (Raman et al.,

2005).

Figure 4: Schiff base synthesized from 4-aminoantipyrine and 3-salicylideneacetylacetone

Source: Raman et al., 2005

2.7.4 Electronic Absorption Spectroscopy and Magnetic Moment Measurements

The uv-vis spectroscopy measures the response of a sample to ultraviolet and visible range of

electromagnetic radiation since the molecules and atoms have electronic transitions. Electronic

transitions found in organic compounds include ζ, π and n electrons while d and charge transfer

transitions are found in complexes, the excitation of a molecule from its electronic ground state

to an electronic excited state corresponds to absorption of light in the near-infrared, visible or

ultraviolet regions of the spectrum.

Figure 5: Electronic transitions in organic compounds

Source: Ndidi, 2015

Figure 6: Electronic Transition in Metal Complexes

Source: (Soliman, 1997).

The electronic transitions in organic compounds are usually observed in the 200-400 nm region.

The first 2 bands located in the 204-270 nm is assigned to the excitation of the π-electrons of the

aromatic ring (π→π*). The third band observed within the wavelength range 257-295 nm is

usually due to transition between the π-orbital largely localized on the the central C=N bond. The

fourth band within the wavelength range 305-360 nm is attributed to an inter-molecular charge

transfer. Occasionally a firth band could be observed due to polar solvents within the wavelength

range 435-440 nm ascribed to intermolecular charge transfer between solvent and the molecule

(Soliman, 1997).

The electronic spectra of 4-aminoantipyrine and benzaldehyde in ethanol have been reported

(Issa et al., 2005).

Figure 7: Schiff base derived from 4-aminoantipyrine and benzaldehyde

The ligands showed four main absorptions in ethanol between 200-400 nm. The first (210-234

nm) and second (240-281 nm) were assigned to π→π* transitions of the aromatic ring. The band

at 301-334 nm involved π→π* transitions of the C=O and C=N groups; the longer wavelength

band (325-396 nm) were assigned to an intramolecular charge transfer originating from the 4-

aminoantipyrine ring to the C=O.

2.7.5 Thermal Analysis of Schiff Base Metal Complexes

Thermal analysis (TA) involves a group of techniques in which changes in physical or chemical

properties of the sample are monitored against time or temperature, while the temperature of the

sample is programmed. The temperature program may involve heating or cooling at a fixed rate.

Thermal analyses comprises a wide variety of techniques such as; thermogravimetric analysis

(TGA), differential thermal analysis (DTA), differential scanning calorimetry (DSC), thermal

mechanical analysis (TMA), temperature resolved X-ray diffraction, thermomagnetometry,

thermoconductometry and dilatometry. The most common thermal analysis used are TGA and

DSC. Thermal stability of materials, estimated lifetime of a product, decomposition kinetics of

materials, moisture and volatile content of materials are obtained from the TGA study while the

DSC graph gives the glass transition temperature (Tg), crystallization temperature (Tc), melting

temperature (Tm) and sample purity of the materials.

As thermal energy is supplied to the sample, its enthalpy increases and its temperature rises by

an amount determined, for a given energy input, by the specific heat of the sample. The specific

heat of a material changes slowly with temperature in a particular physical state, but alters

discontinuously at a change of state. The supply of thermal energy may induce physical or

chemical processes in the sample, e.g. melting or decomposition, accompanied by a change in

enthalpy, the latent heat of fusion, heat of reaction and phase transformation.

2.7.6 Molar Conductance

The molar conductance for the complexes measured in 10-3M solution in DMF and chloroform

as solvents at room temperature (29-31ºC). The molar conductivity is applied to help in the

investigation of the geometrical structures of the complexes. Some complexes showed a lower
molar conductivity values in the range 0.03-44.37Scm2mol-1 which indicated their nonelectrolytic

nature. Other complexes found to be a higher electrolyte with the values more than 50cm 2mol-1,

these results is demonstrated that the complexes have a binuclear nature (Kojima et al., 2003).

The molar conductance has been demonstrated to be a very useful tool in the investigation of

electrolytic nature and geometrical structure of inorganic compounds.

2.7.7 Magnetic Susceptibility

Measurements Magnetic susceptibility of the complexes will be measured and magnetic

moments can be calculated. From the magnetic moment values in conjugation with molecular

formulae, geometry (hybridization) of complexes will be determined. The gram magnetic

susceptibility values, the magnetic moment in BM are calculated and presented as data. From the

obtained result, M-L is concluded to be a high spin complex or M-L as a low spin complex

(Spinu and Kriza, 2000). Magnetic susceptibility measurements are used to determine the extent

of electron pairing, the stereochemistry and metal-metal interactions in the complexes.

2.8 Applications of Schiff Base Transition Metal Complexes

Schiff base transition metal complexes in catalysis: A discussion on the catalytic activity of

Schiff base metal complexes in various reactions are outlined in this section.

2.8.1 Oxidation Reactions

Uchida and Katsuki et al., (2001) reported the activity of cationic cobalt (III) salen complexes in

Baeyer–Villiger oxidation of 3-phenyl cyclobutanone with H2 O2 or urea-hydrogen peroxide

adduct. The analogous [Zr(salen)] catalysts are also active in Baeyer– Villiger oxidation of

cyclobutanone derivatives to produce lactones in 75–99% yields and 69–78%in the presence of
H2O2 as an oxidant. Reddy and Thornon et al., (1992) reported that complexes (1) and (2) in

catalyze the oxidation of a range of ketone silylenol ethers to give α-hydroxyketones using

iodosylbenzene as oxidant in acetonitrile at room temperature. Later, Waldemar et al., (1998)

showed that (1) also catalyzes the asymmetric oxidation of silyl ketene acetals in high

enantioselectivity. Nakajima et al., 1986 studied the application of chiral Schiff base complexes

in enantioselectivity sulfide oxidations. Using tetra dentate Schiff base-oxovanadium (IV)

complex, as catalyst, they could achieve an enantioselectivity of 42% in the oxidation of

methylphenyl sulfide to the corresponding sulfoxide.

2.8.2 Epoxidation Reactions

Katsuki et al., (2001) introduced the second-generation Mn-(salen) catalysts have surpassed

Jacobsen’s catalyst in terms of selectivity and activity, but they are not as synthetically

accessible, and this has limited their application, Zhao et al., (1996)The manganese Schiff base

chelate, synthesized by exhibit moderate asymmetric induction (31–74%) in the epoxidation of

decahydronaphthalene with higher turnover number 2728.

2.8.3 Polymerization Reactions:

Aluminum complexes of a series of tridentate Schiff base ligands were found to catalyze the

polymerization of ethylene. A number of pyridyl bis(imide) complexes and phenoxy imines

complexes are used as catalysts in the polymerization of ethylene. Pyridine bis(imines)

complexes of iron(III) and cobalt(II) show significant activity in the polymerization of ethylene

and copolymerization of ethylene with 1-hexene.

2.8.4 Hydrogenation Reactions

Venkatachalam et al., (2006) also reported the transfer hydrogenation of imines to amines

mediated by ruthenium (III) bis-bidentate Schiff base complexes. The catalytic activity in the

transfer hydrogenation of aliphatic and aromatic ketones in the presence of isopropanol and

KOH has been investigated with ruthenium(III) Schiff base complexes of general formula

[RuX(EPh3)(LL’)] where X = Cl or Br, E = P or As and LL’ = [ONNO] donor of the heterocyclic

Schiff base ligands (Joginder et al.,2017).

2.9 Antimicrobial Activities of Schiff Base Ligands

The free Schiff’s base ligands and their metal complexes are screened in-vitro for their

antimicrobial activities against bacterial strains and fungal strains using agar well diffusion

method. The samples may dissolve in DMSO or in appropriate solvent to make a concentration

of 100 g/ml Schiff’s base ligands and their complexes and 2 mg/ml for standards (Mohammed,

2014). The inoculums (1 x 108 Cfu/mL) are added to molten agar and the media were shaken to

disperse the microorganisms. Four millimeters diameter wells were punched in the agar with a

sterile cork borer. 10 -1 of the sample was introduced in the well. Imipenem was used as positive

reference for bacterial strains while miconazole was used for fungal strains. Antimicrobial

activity was evaluated by measuring the diameter of inhibition zone in mm. Most of the results

of the researchers indicated that the Schiff’s base ligands do have undersized activity, where as

their complexes showed more activity against the same organisms under identical experimental

conditions.
REFRENCES

Tim Soderberg (2010) Organic Chemistry With a Biological Emphasis. University of Minnesota

Morris.

J. M. Gemi, C. Biles, J. B. Keiser, S. M. Poppe, S. M. Swaney, W. G. Tarapley, D. L. Romeso

and Y. Yage, J. Med. Chem., 43, 1034 (2004).

H. Keypour, M. Rezaeivala, L. Valencia, P. Perez Lourido and H. Raza Khavasi, Polyhedron, 28,

3755 (2009).

Babu HV, Venkateswara Rao A, Ravindar V, et al. (2017) Synthesis, Structural

Characterization, and Antibacterial Activity of Iron (II) New Schiff-base Compounds. Acta

Chim Pharm Indica. 7(1):105. Trade Science International.

G. C. Pier "Metal-salen schiff base complexes in catalysis practical aspects," Tutorial Review,

pp. 119, 67-88, 2004

R. Minna, "Schiff base complexes and their assemblies on surface laboratory of inorganic

chemistry," p. 21, 2007.

H. Keypour, S. Salehzadeh, and R. V. Parish, "Synthesis of two potentially heptadentate (N4O3)

schiff base ligand derived from condensation of tris-(3-amino propyl)amine and salicylaldehyde
or 4-hydroxysalicylaldehyde Ni(II) and Cu(II) complexes of the former ligand," J. Molecules,

vol. 7, pp. 140-144, 2002

Y. Ali Mohammed, "Chemical synthesis, spectral characterization and antimicrobial studies on

complexes of Ni(II), Cu(II) and Zn(II) with N, N-di (o-hydroxybenzenoylmethylene)

ethylenediamine," American Journal of BioScience. Special Issue: Chemical Biology, vol. 2, pp.

22-34, 2014.

C. Spinu and A. Kriza, "Co(II), ni(II) and cu(II) complexes of bidentate schiff bases," Acta

Chimica Solvenica, vol. 47, 2000.

M. Kojima, H. Taguchi, M. Tsuchimoto, and K. Nakajima, Coordination Chemistry Reviews,

vol. 237, pp. 183-196, 2003.

T Uchida, T Katsuki (2001) Tetrahedron Letters 42: 6911-6914.

Watanabe, T Uchida, K Ito, T Katsuki (2002) Tetrahedron Letters 43: 4481-4485.

DR Reddy, ER Thornton (1992) A very mild, catalytic and versatile procedure for α-oxidation of

ketone silyl enol ethers using (salen) manganese(III) complexes; a new, chiral complex giving

asymmetric induction. A possible model for selective biochemical oxidative reactions through

enol formation. Journal of Chemical Society Chemical Communication 2: 172-173.

A Wald mar, TF Rainer, RS Viet, RS M Chantu (1998) Journal of American Chemical Society

120: 708-714.
K Nakajima, K Kojima, T Aoyama, J Fujita (1986) Chemistry Letters 1483-1486.

H Nishikori, C Ohta, T Katsuki (2000) Synlett 1557-1560.

T Uchida, R Irie, T Katsuki (1999) Chiral (ON) Ru-salen catalyzed cyclopropanation: High cis-

and enantio-selectivity. Synlett 7: 1166- 1168.

T Katsuki (2004) Unique asymmetric catalysis of cis-β metal complexes of salen and its related

Schiff-base ligands. Chemical Society Reviews 33: 437-444.

SH Zhao, PR Ortiz, BA Keys, KG Davenport (1996) Tetrahedron Letters 2725.

RG Cavell, K Aparna, RP Kamalesh Babu, Q Wang (2002) Journal of Molecular Catalysis A

Chemical 137-143.

GJP Britovsek, VC Gibson, BS Kimberly, PJ Maddox, SJ Mc Tavish, et al. (1998) Novel olefin

polymerization catalysts based on iron and cobalt. Chemical Communications 7: 849-850.

Joginder K, Amit Rai, Vinit R. A Comprehensive Review on the Pharmacological Activity of

Schiff Base Containing Derivatives. Organic & Medicinal Chem IJ. 2017; 1(3): 555564.

0. GJP Britovsek, VC Gibson, DF Wass (1999) The Search for NewGeneration Olefin

Polymerization Catalysts: Life beyond Metallocenes. Angewandte Chemie International Edition

38(4): 428-447.

S Matsui, T Fujita (2001) Catalysis Today 63-73. 32. Y Nakayama, H Bando, Y Sonobe, T

Fujita (2004) Olefin polymerization behavior of bis(phenoxy-imine) Zr, Ti, and V complexes

with MgCl2 - based co catalysts. Journal of Molecular Catalysis A Chemical 213910: 141-150.
R Souane, F Isel, F Peruch, PJ Lutz. (2002) Pyridine bis(imine) cobalt or iron complexes for

ethylene and 1-hexene (co)polymerization. Comptes Rendus Chimie 5(1): 43-48.

G Venkatachalam, R Ramesh (2005) Ruthenium(III) Schiff base complexes of [ONNO]-type

mediated transfer hydrogenation of ketones. Inorganic Chemistry Communications 8(11): 1009-

1013.

G Venkatachalam, R Ramesh (2006) Ruthenium(III) bis-bidentate Schiff base complexes

mediated transfer hydrogenation of imines. Inorganic Chemistry Communications 9(7): 703-707.