CHAPTER 1

INTRODUCTION
___________________________________________
In coordination compound, a small number of molecules or ions called ligands
surround a central metal atom or ion. Each ligand shares a pair of electrons with the metal.
The majority of ligands are anions or neutral molecules that can donate at least one pair of
electron. With increasing knowledge about the coordination compounds and
understanding the structure and nature of bonding of it, has gained importance in the large
amount of synthetic work done in recent years. The participation of metal ions in the
structure and function of biological system has now been documented, demonstrating the
versatility of the coordination compounds.
It is appropriate to present a brief account of modern theories of coordinate bond
which provided somewhat more refined approach in understanding the nature of chemical
bonds in complex compounds. It was Alfred Werner’s1classical idea of coordination
bond in 1893 which gave a great agreement to the development of coordination chemistry.
In the preliminary stages of the understanding of the structure of complexes including
stereochemistry and isomerism of many compounds, Werners theory explained some of
the properties. The Theory postulated primary and secondary valences in compounds and
complexes. The bonds between the ligand and metal ion are due to the secondary valences
of metal ions. Sidgewick, Fajans and others2, cleared the idea regarding primary and
secondary valences in compounds and complexes emphasized the importance of electron
pair bonds. This theory introduced the idea that, ligands contain unshared pairs of
electrons which could be used to form coordinate bond with the metal ion.
After the Werner's theory, Pauling has used Valence Bond Theory to explain the
bonding in coordination compounds with the use of quantum mechanical approach and
concept of hybridization. The most significant theoretical advance in coordination
chemistry is the development of the Crystal Field Theory. This theory was proposed by
Bethe in 1930 and exploit by Van Vleck3. In this theory, ligand and metal ion are
considered as point charges and the bond between the central metal ion and the ligands is
considered ionic. The central metal ion has five d-orbitals of the same energy
(degenerate). The degeneracy is destroyed when the ligands approach the metal ion and
split the d-orbitals into two sets ‘t2g’ and ‘eg’. The significance of this theory is the correct

1
explanation of the electronic spectra, stereochemistry and magnetic properties. The main
draw back of this theory is that it considers the metal-ligand bond to be purely
electrostatic. However; experimental evidences show that the complexes exhibit some
covalent character also. Therefore, ligand field theory, is introduced which is the
modification of the crystal field theory. In this theory, the covalent character is also
incorporated.

1.2 SCHIFF BASE AS A LIGAND

The Schiff bases are those organic molecules which contain azomethine group
(-CH=N-) capable of donating lone pair of electrons. The Schiff bases are generally
synthesized by condensation of the primary amine (RNH2) with compounds having active
carbonyl group. They are also well known by the name of anils and amines. The general
formula of the Schiff basis is (R-CH=N-R’) Where Rand R’ are alkyl, aryl, cyclohexyl or
heterocyclic groups.
The general reaction for formation of Schiff base can be represented as:

H H

R C O + H2NR' R C N R' + H2O

Ketone Amine Schiff base

This mechanism was first observed in the case of aniline and benzaldehyde as
early as 1850 by Laurent and Gerhart4. Later Schiff5 found that many aromatic and
aliphatic aldehydes condense with aniline in similar way.
Due to the flexible nature, easy proton donating property and with number of
donating group, the study of Schiff and their complexes with transition metals, lanthanides
and radioactive metals is flourished since few decades. Schiff base ligands show a number
of sites for binding that lead to higher coordination polyhedra and cause greater kinetic
and thermodynamic stability.

1.3 General behaviour of Schiff bases :

Schiff bases are weak bases and are readily hydrolysed by dilute mineral Acids,
but not by aqueous alkalis. They form salts by coordination of the Electrons on nitrogen
atom of azomethine group. The Schiff bases derived from lower aliphatic aldehydes are

2
less stable than those derived from aromatic aldehydes. Schiff bases derived from
Formaldehyde exhibit tendency to undergo polymerization another reactions.
The Schiff bases derived from aryl amines are more stable than their aliphatic
analogues. Aliphatic Schiff bases are difficult to isolate due to their tendency to
polymerize. A large number of anils have been reported to be photochromic6 or
thermodynamic in crystalline stage. Cohen7,8 et al inferred that presence of hydroxyl group
is a structural requirements for phtotochromism of anils in low temperature solutions. In
contrast rigid solutions including p-hydroxy and o-methoxy substituents are not
photocromic. It is well known fact that Schiff bases containing multiple donor sites play a
key role in investigation of geometrical structure of coordination compounds. By changing
the nature of position of donor groups and atoms, it is possible to control size of chelating
ring and study the effect of substitution.
The Schiff base us considered as useful chelating agent when suitable Functional
group like (-OH), (-SH), (-NO2) etc., are present, sufficiently close to the azomethine
group. Generally Schiff bases are insoluble in water. In marked contrast to this McCarthy9
et al reported Schiff bases obtained by condensation of ethylene diamine or triethylene
diamine with acetyacetone to be dissociating in water.
Some of the Schiff bases are readily hydrolyzed back o-amine and Aldehyde.
Hydrolysis of Schiff bases generally disrupts coordination structures. Thus any factor
leading to increase in stability of coordinated structure decreases tendency for hydrolysis.
Hence chelate derived from metals high in stability lie Pd(II) and Cu (II) are more
resistant to hydrolysis than those chelates derived from metals low in stability.
Many such factors are responsible to make Schiff bases excellent Chelating agents
to be used as potential analytical reagents. Martell and his group also prepared six Co(II)
complexes of tridentate and pentadentate N-benzyltriamine ligands, and also their
dioxygen complexes. A study of the stabilities of these complexes was also made.
The ESR and electronic spectra of low-spin Co(II) complexes with some
quadridentate Schiff bases of the N2S2 type were measured by Nishida and his group.
Analysis of the ESR parameters led to the conclusion that an unpaired electron is in the
dyz orbital of the cobalt atom. Based on this, the absorption at 10,000 cm-1 was attributed
to the dx2-y2, dyz transition. The magnetic moments of cobalt (II) complexes with H2 (nsen)
= N, N’ – bis (1-phenyl -2-thiobenzoylvinyl) ethylenediamine; H2 (nstn) = N,N’ –bis (1-
phenyl -2- thiobezoylvinvyl) trimethylene – diamine; and H2 (nspn) = N,N’-bis(1-phenyl
-2- thiobezoylvinyl) ropylenediamine were found to be in the range 2.2 -2.3 B.M. at room

3
temperature, indicating that all the complexes are of the low-spin type. Biradar and
coworkers synthesized Co (II) complexes of Schiff bases derived from vanillin and
ethylenediamine, propylenediamine, o-phenylenediamine or bezidine. The crystal field
splitting energy 10Dq and Racah parameter (B) has been deduced. The Racah parameter
values (B) were of the order of 60-70% of the free ion value (967cm-1), this was reported
to be due to considerable orbital overlap. The Values at room temperature were observed
in the range of 4.2-4.6 B.M. Tetrahedral geometry was proposed for Co (II) complexes on
the basis of electronic spectral data and magnetic susceptibility measurements.
A series of Ni (II) complexes containing macrocyclic and linear Schiff bases were
prepared by template condensation of diamines with 4-thiaheptane-2,6-dione in the
presence of Ni (II) salts by Tandon and Larkworthy. Purple nickel (II) complexes were
obtained having a highly distorted octahedral stereochemistry. These complexes were
found to have effective magnetic moments in the range 2.82-3.11 B.M. at room
temperature. Saha10 et al reported orange red Ni(II) complexes of four new tridentate
Schiff bases with (ONN) donor sequence derived from salicylaldehyde, 5-substituted
salicylaldehyde and nitroaminoguanidine.

R CH=N NH C NH NO2

NH
OH

where = R=H,5-Cl,5-Br,or5- NO2

All the Nickel (II) complexes, [NiR-SBX] nH2O, (X2O, py, and -pic) were characterized
by various techniques. All the orange-red Nickel(II) complexes were diamagnetic as
ascertained from magnetic susceptibility measurements (Gouy method using G.R
CuSO4..5H2O as calibrant). Saha10 et al attributed principle absorption band by Ni(II)
complexes in UV –Visible spectra to 1A1 -1B1 transition as present in a square - planar
geometry.
Dolphin11 et al carried out facile template synthesis of Nickel (II) complexes of
dibenzotetraaza[14] annulenes by condensing diamines with Diketones or 1,5 –
benzodiazepinium salts in the presence of Ni (II) salt. Complexes with substituents on the
benzenoid rings were found to be more stable in organic solvents than the complexes
substituted on the demined rings. Hypsochromic shifts were observed in the UV spectra of

4
the complexes which were correlate with the degree of substitution in the dimine
substituted complexes. Minor shifts were observed in the UV spectra for phenylene
substituted complexes.
In continuation of their work12 they also prepared [N-N1-(1-3-propanediylidene)
bis (1,2 –benzenediaminato)] nickel(II) complexes by metal template condensation of
diketone or ketoacetals with an appropriate o-phenylene diamine in the presence of a
Ni(II) salt. Evidence was presented which indicated that the monoanils participated as
intermediates in the metal template condensation of these diamines with diketones.
A number of Ni(II) complexes with tridentate Schiff base ligands with a (-N2O)
donor set and coordinating (NNN-) and (SCN) anions have been synthesized and
characterized by analytical, spectroscopic and electrochemical techniques by Malik13 et al.
X

OH X,H,R=R'= CH3
N X=R=H,R;= C2H5
X=Br,R=H,R'= C2H5

R' R'

X-Ray structure analyses of Ni(II) complexes show that the nickel atom has a square
planar geometry. Thermogravimetric studies show multiples step decomposition and
electrochemical studies indicated that the complexes were irreversible oxidized to Ni (II)
species.

5
 CHAPTER 2

EXPERIMENTAL

___________________________________________
1) APPARATUS: Beaker, glass rod, measuring flask, pipette, round bottom flaks, G3
crucible, Whattman filter paper 1, dropper, test tubes, ‘A’  grade  pipettes  and  burettes 
were  used  throughout  the  experimental  work.  All  the  apparatus  were  standard 
analytical methods.
2)  CHEMICALS
Water    ‐  Entire  experimental  work  was  carried  out  by  using  distilled  water.  It  has 
prepared by distilling deionised Water in presence of potassium permanganate and 
two pellets of potassium hydroxide.   

Following Aldehyde, metal Salts were used for the Synthesis of Schiff base and metal
complex.
Table 1 

  No.  Name  Grade 

 1  P‐toluedine A.R.

 2  1‐Hydroxy‐2‐ A.R.

naphthaldehyde 
 3  Nickel Chloride G.R.
 4  Cobaltus Chloride G.R.

 5  Dimethyl glyoxime G.R

 6  Hydrogen  peroxide A.R.

 7  Cobalt nitrate A.R

                  
 

6
1)Solvents acids were used during experimental work

Table 2 

.No. Solvent Acid Grade

1  Ethanol HydrochloricAcid A.R.

2  Dimethyl  Nitric Acid A.R
Sulphoxide 
3   Acetone Perchloric Acid A.R.
Table 3 
Range  PH at 250 C  Calibrate used 
Acidic Range  4.20 0.05 M Potassium hydrogen phthalate 
Basic  Range  9.18 0.05 M Borax
 
 
 3) INSTRUMENTS:
Balance - An Analytical balance manufactured by Shimadzu of 0.001 mg. Sensitivity was
used, for Sample, weighing up to 200 mg more. For Sample weighing less than 100 mg, a
semi micro balance supplied by CITIZEN Scale (I) PVT.LTD
pH Meter ­    At various Stage in the experimental work, pH measurements were done
using pH meter.. For accurate measurement of hydrogen ion concentration.
Instrument - The instrument was supplied by M / S Elico pvt. Ltd, with model no LI –
120.
Standardization: - The pH meter was standardized using following solutions. 

CONDUCTIVITY METER
Principle  ­  The measurement of molar conductance gives information about the
electrolytic behaviour of a compound. The electrical Conductivity is due to movement of
ions through the Solution under the influence of an imposed force which could be an
electric field or a concentration gradient. 
Instrument - The instrument used was supplied by ELICO CM 180. Digital conductivity
meter has various ranges from millimhos to micromhos.
Standardization - The instrument was standardized by using 0.1 N KCl solution.
 
 

7
Table 4

Sr. No. INSTRUMENT MODEL Company

1 Conductometry, U-V2401PC UV Brooker Biospin
visible double beam recording spectro
photometer,

2 IR Spectroscopy FTIR Perkin Elmer Spectro

one,

3 GCMS Mass Thermo Polaris Q mass

spectrometer Ultra trace GC,

4 TGA-DTA TG-DTA Perkin Elmer Pyris

diamond
5 Atomic absorption spectroscopy AAS Perkin Elmer Analyst
200

2.1 IR SPECROSCOPY :

Introduction:
Infrared (IR) spectroscopy is one of the most common spectroscopic techniques
used by organic and inorganic chemists. Simply, it is the absorption measurement of
different IR frequencies by a sample positioned in the path of an IR beam. The main goal
of IR spectroscopic analysis is to determine the chemical functional groups in the sample.
Different functional groups absorb characteristic frequencies of IR radiation. Using
various sampling accessories, IR spectrometers can accept a wide range of sample types
such as gases, liquids, and solids. Thus, IR spectroscopy is an important and popular tool
for structural elucidation and compound identification.
Fourier transform spectroscopy is a measurement technique whereby spectra are
collected based on measurements of the coherence of a radiative source, using time-
domain or space-domain measurements of the electromagnetic radiation or other type of
radiation. It can be applied to a variety of types of spectroscopy including optical
spectroscopy, infrared spectroscopy (FT IR), Fourier transform (FT) nuclear magnetic
resonance, mass spectrometry and electron spin resonance spectroscopy. There are several
methods for measuring the temporal coherence of the light, including the continuous
wave. Michelson or Fourier transform spectrometer and the pulsed Fourier transform
spectrograph (which is more sensitive and has a much shorter sampling time than

8
conventional spectroscopic techniques, but is only applicable in a laboratory
environment). The goal of any absorption spectroscopy (FTIR) is to measure how well a
sample absorbs or transmits light at each different wavelength. The most straightforward
way to do this is to shine a monochromatic light beam through a sample, measure how
much of the light is absorbed, and repeat for each different wavelength. (This is how UV-
Vis spectrometers work, for example.)

Fourier transform spectroscopy is a less intuitive way to get the same information.
Rather than passing a monochromatic beam of light through the sample, this technique
passes a beam containing many different frequencies of light at once, and measures how
much of that beam is absorbed by the sample. Next, the beam is modified to contain a
different combination of frequencies, giving a second data point. This process is repeated
many times. Afterwards, a computer takes all this data and works backwards to infer what
the absorption is at each wavelength. The beam described above is generated by starting
with a broadband light source one containing the full spectrum of wavelengths to be
measured. The light shines into a certain configuration of mirrors that allows some
wavelengths to pass through but blocks others (due to wave interference). The beam is
modified for each new data point by moving one of the mirrors; this changes the set of
wavelengths that pass through.

As mentioned, computer processing is required to turn the raw data (light

absorption for each mirror position) into the desired result (light absorption for each
wavelength). The processing required turns out to be a common algorithm called the
Fourier transform (hence the name, "Fourier transform spectroscopy"). The raw data is
sometimes called an "interferogram".An invaluable tool in organic structure determination
and verification involves the class of electromagnetic (EM) radiation with frequencies
between 4000 and 400 cm-1 (wave numbers). The category of EM radiation is termed
infrared (IR) radiation, and its application to organic chemistry known as IR spectroscopy.
Radiation in this region can be utilized in organic structure determination by making use
of the fact that it is absorbed by interatomic bonds in organic compounds. Chemical bonds
in different environments will absorb varying intensities and at varying frequencies. Thus
IR spectroscopy involves collecting absorption information and analysing it in the form of
a spectrum17.

9
2.2 ULTRA - VIOLET SPECTROSCOPY:

The ultra violet light (200-400) is obtained by the hydrogen discharge lamp. Glass
absorbs ultra violet radiation .Therefore the prism and cell must be made up of quartz. The
solvents generally used are water, 95% ethanol, hexane etc.
UV-VIS spectroscopy is a method which uses light with wavelengths ranging from
400 to 800 nm. It is in this region of energy space that molecules undergo electronic
transitions. By bombarding atoms or molecules with radiation, it causes the “redirection of
the radiation and/or the transition between energy levels of the atoms or molecules.” The
transition with transfer of energy is absorption. Absorption is proportional to the
concentration of a compound in a solution. The Beer-Lambert Law gives the relationship
between absorbance and concentration. “The analytical utilization of atomic absorption
rests on the principle that the total absorption of light, expressed as log I0 / I is directly
proportional to the concentration and absorptivity.”

The Beer-Lambert Law states that the log of the ratio of the intensities is equal to
the negative of the absorptivity coefficient (-ε) times the concentration (C) multiplied by
the path length (b).
log [I / I0] = - ε C b ............………(1)

This equation is due to the fact that if light is passed through a sample, some of it
will be absorbed and some will be let through (transmitted). Therefore, there are 2
different intensities. I0 is the original intensity, meaning the one that was sent into the
solution. I is the intensity of the light exiting the sample. This is often referred to as
transmittance.
Therefore, the equation for transmittance is,

T = [I / I0] …………….(2)

This is what defines absorption, which is the following equation:

A = -log [T] = ε C b …………… (3)

By using UV-VIS spectroscopy, we can determine the pKa of an indicator, which

are weak acids or bases. Our indicator has a protonated and deprotonated form, which

10
absorbs differently at different wavelengths. Since they absorb differently, the absorbance
spectra can be used to determine the value of the pKa17.

2.3 NMR SPECTROSOPY

The 1H NMR spectrum of Schiff base and complex is recovered in DMSO – d6
solvent, position of each proton signal along with the chemical shift (δppm).

Nuclear magnetic resonance (NMR) is a property that magnetic nuclei have in a

magnetic field and applied electromagnetic (EM) pulse or pulses, which cause the nuclei
to absorb energy from the EM pulse and radiate this energy back out. The energy radiated
back out is at a specific resonance frequency which depends on the strength of the
magnetic field and other factors. This allows the observation of specific quantum
mechanical magnetic properties of an atomic nucleus. Many scientific techniques exploit
NMR phenomena to study molecular physics, crystals and non-crystalline materials
through NMR spectroscopy. NMR is also routinely used in advanced medical imaging
techniques, such as in magnetic resonance imaging (MRI).

All stable nucleus that contain an odd number of protons and/or of neutrons (see
Isotope) have an intrinsic magnetic moment and angular momentum, in other words a spin
> 0, while all nucleus with even numbers of both have spin 0. The most commonly studied
nuclei are 1H. A key feature of NMR is that the resonance frequency of a particular
substance is directly proportional to the strength of the applied magnetic field. It is this
feature that is exploited in imaging techniques; if a sample is placed in a non-uniform
magnetic field then the resonance frequencies of the sample's nuclei depend on where in
the field they are located. Since the resolution of the imaging techniques depends on how
big the gradient of the field is many efforts are made to develop more powerful magnets,
often using superconductors. The effectiveness of NMR can also be improved using
hyperpolarization, and/or using two-dimensional, three-dimensional and higher dimension
multi-frequency techniques.

The principle of NMR usually involves two sequential steps:

• The alignment (polarization) of the magnetic nuclear spins in an applied, constant

magnetic field H0.

11
• The perturbation of this alignment of the nuclear spins by employing an electro-
magnetic, usually radio frequency (RF) pulse. The required perturbing frequency is
dependent upon the static magnetic field (H0) and the nuclei of observation.

2.4 Mass spectrometry (MS) is an analytical technique for the determination of the
elemental composition of a sample or molecule. It is also used for elucidating the chemical
structures of molecules, such as peptides and other chemical compounds. The MS
principle consists of ionizing chemical compounds to generate charged molecules or
molecule fragments and measurement of their mass-to-charge ratios. In a typical MS
procedure:

1. A sample is loaded onto the MS instrument, and undergoes vaporization.

2. The components of the sample are ionized by one of a variety of methods (e.g., by
impacting them with an electron beam), which results in the formation of positively
charged particles (ions)
3. The positive ions are then accelerated by a magnetic field
4. Computation of the mass-to-charge ratio of the particles based on the details of motion
of the ions as they transit through electromagnetic fields, and
5. Detection of the ions, which in step 4 were sorted according to m/z.

MS instruments consist of three modules: an ion source, which can convert gas
phase sample molecules into ions (or, in the case of electrospray ionization, move ions
that exist in solution into the gas phase); a mass analyzer, which sorts the ions by their
masses by applying electromagnetic fields; and a detector, which measures the value of
an indicator quantity and thus provides data for calculating the abundances of each ion
present. The technique has both qualitative and quantitative uses. These include
identifying unknown compounds, determining the isotopic composition of elements in a
molecule, and determining the structure of a compound by observing its fragmentation.
Other uses include quantifying the amount of a compound in a sample or studying the
fundamentals of gas phase ion chemistry (the chemistry of ions and neutrals in a vacuum).
MS is now in very common use in analytical laboratories that study physical, chemical, or
biological properties of a great variety of compounds.

12
2.5 DIFFERNTIAL THERMAL ANALYSIS

DTA is a technique in which the difference in temperature in between substance

and reference material is measured as a function of temperature while the substance and
reference material is subjected to controlled temperature program.
Usually the temperature program involve heating of the sample and reference
material in such a way that temperature of sample Ts increase linearly with time the
difference temperature ΔT = Tr – Ts is then monitored and then plotted against sample
temperature to give differential thermogram .

¾ THERMO GRAVIMETRIC ANALYSIS

Thermogravimetric Analysis or TGA is a type of testing that is performed on

samples to determine changes in weight in relation to change in temperature. Such
analysis relies on a high degree of precision in three measurements: weight, temperature,
and temperature change. As many weight loss curves look similar, the weight loss curve
may require transformation before results may be interpreted. A derivative weight loss
curve can be used to tell the point at which weight loss is most apparent. Again,
interpretation is limited without further modifications and deconvolution of the
overlapping peaks may be required. TGA is commonly employed in research and testing
to determine characteristics of materials such as polymers, to determine degradation
temperatures, absorbed moisture content of materials, the level of inorganic and organic
components in materials, decomposition points of explosives, and solvent residues. It is
also often used to estimate the corrosion kinetics in high temperature oxidation.

Simultaneous TGA-DTA/DSC measures both heat flow and weight changes

(TGA) in a material as a function of temperature or time in a controlled atmosphere.
Simultaneous measurement of these two material properties not only improves
productivity but also simplifies interpretation of the results. The complimentary
information obtained allows differentiation between endothermic and exothermic events
which have no associated weight loss (e.g., melting and crystallization) and those which
involve a weight loss (e.g., degradation).The analyzer usually consists of a high-precision
balance with a pan (generally platinum) loaded with the sample. The pan is placed in a
small electrically heated oven with a thermocouple to accurately measure the temperature.

13
The atmosphere may be purged with an inert gas to prevent oxidation or other undesired
reactions. A computer is used to control the instrument.

Analysis is carried out by raising the temperature gradually and plotting weight
against temperature. The temperature in many testing methods routinely reaches 1000°C
or greater, but the oven is so greatly insulated that an operator would not be aware of any
change in temperature even if standing directly in front of the device. After the data is
obtained, curve smoothing and other operations may be done such as to find the exact
points of inflection. In thermo gravimetric analysis the mass of sample in controlled
atmosphere recorded continuously as a function of temperature or time as the temperature
of sample is increased. (Usually linearly with time). A plot of mass or mass percent as a
function of time is called thermogram or thermal decomposition. In this analysis first we
are studying the weight loss of the water molecule then we observed loss in the ligand and
at the end we study weight loss of the metal oxide.

14
2.1 SYNTHESIS OF SCHIFF BASE
REQUIREMENT: 2-Hydroxy-1-naphthaldehyde, P-toluedine
PROCEDURE:
¾ Take 0.100g of 2-hydroxy-1-naphthaldehyde and 0.622g of P-toluedine.
¾ Dissolve individually in little amount of ethyl alcohol. Mix both the solution to each
other in hot condition in round bottom flask.
¾ Attach condenser to it, reflux the mixture for about 4 to5 hrs, if precipitate does not
come then adjust pH = 5 reflux for some time. Filter the solution through Whattman
filter paper, give washing with cold water and dry at 100°C.

REACTION:

CH3

CHO CH N CH3
Alc.
+ Reflux
OH 5-6 hrs. OH
NH2

2-Hxydroxy -1- p- toluedine Schiff base

Napthaldehyde

THEORETICAL YIELD:

Molecular weight of P-toluedine = molecular weight of 2Hydroxy-

1-naphthaldehyde

262.35 g = 172.199g
X g = 1g
X = 1.522g
Practical yield = 1.3217g

% yield of Schiff base = __Practical yield X 100

Theoretical yield
= 1.3217 X 100
1.522
= 86.80%
RESULT:
1. Theoretical yield of Schiff base = 1.3217g
2. Practical yield of Schiff base = 1.3217g
3. % yield of complex = 86.80%
4. Melting point if Schiff base = 138°c

15
2.2 SYNHTESIS OF Ni COMPLEX

REQUIREMENT : NiCl2.6H2O, Schiff base

PROCEDURE:
¾ Take 0.1g of metal chloride and required amount of Schiff base. Dissolve both the
content separately in beaker ,boil for some time
¾ Mix both the solution in round bottom flask and reflux for few hours (if precipitate
does not come) then adjust pH = 5.8
¾ Then pour this solution in ice with continuously stirring. Allow this mixture cool for
some time.
¾ Filter the solution through Whattman filter paper, give washing with cold water and
dry at 100°C in a oven.
REACTION:
H

NiCl2 . 6 H2O
C N CH3 +
NICKEL CHLORIDE

OH
SCHIFF BASE
REFLUX FOR
2-3 hrs

C N CH3
Cl
O
Ni
O
Cl
H3C N C

16
THEORETICAL YIELD :

Chemical reaction,
NiCl2.6H2O + C2H5OH + 20%NH3 → Ni[L2Cl2]
58.71g of Ni = 651.71G of Ni[L2Cl2] complex
Xg = 0.3 g
Xg = 3.331g
Practical yield = 1.278g
% yield of complex = Practical yield X 100
Theoretical yield
= 1.278 X 100
3.331
= 38.36%

RESULT:
1. Theoretical yield of complex = 3.331 g
2. Practical yield of complex = 1.278g
3. % yield of complex = 38.36%
4. Melting pot of complex = 284°c

2.3 SYNTHESIS OF Co COMPLEX

REQUIREMENT : CoCl2.6H2O ,Schiff base

PROCEDURE:

¾ Take 0.1g of metal chloride and add require amount of Schiff base dissolve in
separate beaker in ethyl alcohol .Mix both the solutions in hot condition to each
other. Reflux for few hours.
¾ Adjust pH at 5.8 reflux for few minutes and pour in ice cold water.
¾ Filter through whattman filter paper give washing with cold water and dry at
100°C in oven.

17
REACTION:
H

C N CH3 + CoCl2 . 6 H2O

COBALTOUS CHLORIDE
OH

SCHIFF BASE
REFLUX FOR
2-3 hrs

C N CH3
Cl
O
Co
O OH2
H3C N C

H
Co COMPLEX

THEORETICAL YIELD:

Molecular weight of Co = Molecular weight of complex

58.93g = 634.43g
0.2 g = Xg
Xg = 2.15g
Practical yield = 0.868g
% yield of complex = Practical yield X100
Theoretical yield
= 0.8688 X 100
2.15
= 40.20%

RESULT:
1. Theoretical yield of complex = 2.15 g
2. Practical yield of complex = 0.8688g
3. % yield of complex = 40.20%
4. Melting point of complex = 250°C

18
 CHAPTER 3
RESULT AND DISCUSSION
3.1 GRAVIMETRY:

ANALYSIS OF NICKEL:

¾ Take 0.033g of complex and 5 cm3 of HCl and heat nearly to dryness, then add 20
cm3 of distilled water to extract Ni metal from the solution.
¾ From same solution pipette out require amount of (25 cm3) solution add 20 cm3 of 1%
DMG and then add 1:1 NH3 drop wise till get red colour or pink colour precipitate.
¾ Filter the precipitate through G3 crucible. Dry at 110°C and weigh.

Observation and calculation:

Theoretical % of Ni in Complex = weight of Ni metal x100

Weight of complex
= 58.71 x100
651.71
% of Ni metal = 9.00%
1. Weight of empty crucible = 29.67g
2. Weight of crucible + residue = 29.68g
3. Weight of residue = 0.0098g
Weight of Ni(DMG)2g = Weight of Ni metal
288.71g = 58.71g
0.0098g = Xg
Xg = 0.0020g
% of Ni metal = Amount of Ni X100
Weight of complex
= 0.002 X 100
0.0250
= 8.09%
Result : % of Ni metal in complex = 8.09%
Observed % of the Ni complex = 9.04%

19
3.2 Analysis Of Co By Atomic Absorption Spectroscopy
Molecular weight of Co complex = molecular weight of Co
634.43g = 58.933g
Xg = 10 ppm
Xg = 634.34 X0.10
58.933
= 1.076 mg of complex
Contain 0.1 mg of Co(II)
After proper treatment dilute this solution to 50 cm3 to get 100 ppm solution,
from that solution take 1 cm3 dilute to 50 cm3 to get 2 ppm solution.
From that 2 ppm solution prepare flowing calibration curve,
TABLE 5

Sr. No Conc. Co(II) in ppm Absorbance

(μg/cm3)
1 1 0.068
2 2 0.152
3 3 0.231
Sample - 1.735

Abs. coefficient = 0.996928

Slope = 0.07617

Calculation :

Theoretical Co (II) in complex:

Molecular weight of complex = Molecular weight of Co

634.43g = 58.933g
553.819g = X g mg Co(II)
Xg = 58.9332 X 53.81
634.43
= 4.99 mg Co(II)
% of Co complex = 4.99 mg Co(II)
53.819
= 9.28 %
SAMPLE READING = 1.735 μg/cm3

20
1.735 μg Co in 50 cm3 of solution
Amount of Co (II) in 50 cm3 of solution = 1.753 X 50
= 86.50 μg of Co (II)
3
86. 50 μg in 1 cm of stock solution,
Main stock solution contain = 86.50 X 50
= 4325 μg of Co(II)
= 4.32 mg of Co(II)
Practical % of Co in complex = _4.32 X 100
53.88
= 8.03%
Result : % of Co metal in complex = 8.03%
Observed % of the Co complex = 9.43%

3.3 ANALYSIS OF CHLORINE BY VOLHARD'S METHODS

PROCEDURE:

1. Take 10 cm3 of 0.05 N of AgNO3 in a conical flask to which add 5 cm3 of 6 N

HNO3 solution and 1 cm3 of ferric ammonium sulphate indicator.
2. Titrate this solution against ~0.05 N NH4SCN solution with vigorous shaking.
3. The solution turns reddish brown from colourless indicating the end point.

REACTION:
AgSCN + NH4NO3
NH4SCN + AgNO3

Estimation of Cl

1. Take 15 cm3 of 0.05N AgNO3 in a conical flask to this add 25 -35 mg of complex
and 5cm3 of 6N HNO3
2. Heat this solution till boil to that solution add 1 cm3 ferric ammonium sulphate
indicator.
3. Titrate this solution against 0.05 N NH4SCN.
4. The solution will turn reddish brown from colourless indicating the end point of
the reaction.

21
Standardisation of NH4SCN

1. Solution in burette : ~0.05N NH4SCN

2. Solution in flask : 10 cm3 of 0.05 N AgNO3 + 5 cm3 of 6N HNO3
3. Indicator : Ferric ammonium sulphate
4. End point : colour to reddish brown
Constant burette reading = 10 cm3

Normality of NH4SCN

N1V1 = N1V1

NH4SCN = N 2 V2

N1 = 0.05 x 10
10
N1 = 0.05 N

Normality of NH4SCN is 0.05 N

Estimation of Chlorine in Ni complex
1. Solution in burette : 0.05N NH4SCN
2. Solution in flask : 0.025 g of complex + 15 cm3 of AgNO3 + 15 cm3 of
AgNO3 + 15 cm3 of 6N HNO3+ 1 cm3 of Nitrobenzene
3
3. Indicator : 1cm Ferric ammonium sulphate
4. End point : Colourless to reddish brown

FOR Ni complex
Percentage of chlorine in Ni[(C18H14ON)2Cl2]
Theoretical % yield
Molecular weight of complex = 651.71g
% of chlorine = 35.5 X 2
651.71
Practical % yield = 10.89%
Constant burette reading = 28 cm3
Amount of AgNO3 = 15cm3
= 28 X 0.05
= 0.05
= 28 cm3

22
Amount of AgNO3 consumed by chlorine is as follow
= X–Y
= 30-28 cm3
= 2 cm3
% of chlorine in a given complex = 0.05 X 2 X 35.5 X 100
30
= 11.83%

Given Ni complex contain 11.83% of chlorine.

FOR Co(II) complex

Theoretical % of chlorine in Co[ C18H14ON.Cl.H2O]

% of chlorine = 35.5 X 100
634.43
Practical % of chlorine = 5.60%

Constant burette reading = 11.6 cm3

Amount of AgNO3 added = 12 cm3
= 11.6 X 0.05
0.05
= 11.6 cm3
Amount chlorine consumed = X – Y cm3
= 12- 11.6 cm3
= 0.4 cm3
% of chlorine = 0.05 X 0.4X 35.5 X 100
12
= 6.09%

Given Co complex contain 6.09% of chlorine.

23
3.4 CONDUCTIVITY

Aim : To determine the conductivity of complexes using Conductometer.

Requirements: 300ppm solution of Schiff base, 300 ppm solution of Co complex, 300
ppm solution of Ni complex.

Observation Table
TABLE 6

Sr. No Ligand and Instrumental

complexes reading
(Scm2mol-1)
1 Schiff base 5.958
2 Ni complex 6.896
3 Co complex 9.886

Interpretation of Results
From above results it is observed that Schiff base, Ni complex and Co complex
are non-electrolyte in nature.

24
IR Interpretation of the Schiff base
The IR spectral data along with approximate assignments are summarized in Table
no.3 to 5. The IR Spectra are reproduced in the Figure no.7 to 9. The IR spectra of the
ligand show a band at 3200-700 cm-1. In ligand L1, ν(OH) stretching frequencies was
observed as broadband at 3450 cm-1. The Schiff base exhibit azomethine ν(C=N) stretching
vibrations band at 1685 – 1620 cm-1 region. Many workers gives prime importance to the
position of ν(C=N) stretching vibration. In present work, the Schiff base L1 azomethine
ν(C=N) bending vibrations bands at 1635 cm-1.
2-Hydroxy-1-naphtha1dehyde and P-toluedine shows absorption band in the
region of 1619 cm-1. The ν(OH) phenolic stretching vibration of the ligands L1 is pointed
in the region 3500-3400 cm-1. Spectra of ligands Ll indicates many absorption bands in
the fingerprint region with intensity varying between strong to weak.

Interpretation of the Ni complex

(1) Stretching Vibration due to Hydroxyl group.
Schiff base under investigation have –OH group as a prominent functional group,
which on deprotonation forms covalent bond with the central metal ion through oxygen
atom. Ligand (L) exhibits wide and broad band in the region 3400 cm-1 to 3500 cm-1,
which can be assigned to stretching υ(OH) vibration due presence of intra molecular
hydrogen bonding. The corresponding IR spectrum of Ni(II) complex do not show any
absorbance in this region, instead a broad band of medium intensity is observed at
3450.4 cm-1, which can be assigned to -OH stretching vibration. We have further
corroborated to the presence of coordinated water molecule by thermal analysis.
(2) Characteristics Stretching Vibration of azomethine group.
The characteristic band due to υ(C=N) vibrations in the ligand (L) is observed as a
strong band at 1619 cm-1 respectively. In case of Ni(II) complexes of (L) the υ(C=N)
stretching vibration are observed at 1616 cm-1. The υ(C=N) stretching vibration show a
bathochromic shift by 30-40 cm-1 with respect to their band positions in the corresponding
ligands. The shift in υ(C=N) stretching vibration to lower wave number in both the Ni(II)
complexes from its position in the respective region (L) indicate the involvement of
azomethine nitrogen in coordination with the metal ion.

25
(3) Stretching Vibration due to C-H.
The Ni(II) complexes exhibits large number of bands due to C-H stretching C-C
skeletal and C-H bending vibrations. These stretching vibration appear with different
intensity. In Ni(II) complex of L1 the absorption band at 2918 cm-1 with strong intensities
are assigned to in plane deformation with C-H in furan ring.
On critical examination, the spectra of metal complexes show new additional
bands in the lower region on comparison with the band position in the similar region for
the corresponding ligands and the spectra of Ni(II) complex. These additional bands may
be assigned to metal coordination with azomethine nitrogen. The υ(M-N) stretching
vibration is reported to appear around 515 cm-1 while υ(M-O) band is expected to appear
around 421 cm-1.

Interpretation of the Co complex

Stretching Vibration due to Hydroxyl group.
Schiff base under investigation have –OH group as a prominent functional group,
which on deprotonation forms covalent bond with the central metal ion through oxygen
atom. Ligand (L1) exhibits wide and broad band in the region 3400 cm-1 to 3500 cm-1,
which can be assigned to stretching υ(OH) vibration due presence of intra molecular
hydrogen bonding. The corresponding IR spectrum of Co(II) complex do not show any
absorbance in this region, instead a broad band of medium intensity is observed at
3465 cm-1, which can be assigned to -OH stretching vibration. The peak at 830 cm-1 of
coordinated water molecule is observed, hence concluded the presence of coordinated
water molecule.
IR spectrum of Co(II) complex show a broad band of medium intensity at 3465cm-1,
which can be assigned to –OH stretching vibration.
(2) Characteristics Stretching Vibration of azomethine group.
The characteristic band due to υ(C=N) vibrations in the ligands (L) is observed as a
strong band at 1615 cm-1 respectively. The υ(C=N) stretching vibration show a
bathochromic shift by 30 - 40 cm-1 with respect to their band positions in the
corresponding ligands. The shift in υ(C=N) stretching vibration to lower wave number in
both the Co(II) complexes from its position in the respective region (L) indicate the
involvement of azomethine nitrogen in coordination with the metal ion.

26
(3) Stretching Vibration due to C-H.
The Co(II) complexes exhibits large number of bands due to C-H stretching C-C
skeletal and C-H bending vibrations. These stretching vibration appear with different
intensity. In Co(II) complex of L1 the absorption band at 2919 cm-1 with strong intensities
are assigned to in plane deformation with C-H in furan ring.
On critical examination, the spectra of metal complexes show new additional
bands in the lower region on comparison with the band position in the similar region for
the corresponding ligands and the spectra of Co(II) complex. These additional bands may
be assigned to metal coordination with azomethine nitrogen. The υ(M-N) stretching
vibration is reported to appear around 532 cm-1 while υ(M-O) band is expected to appear
around 433 cm-1.

27
4.5 IR SPECTRUM DATA OF SCHIFF BASE

TABLE 7

Sr. No GROUP ν Values (cm-1)

1 C-H(Stretching) 2921.76
2 νC=N 1635.50
3 νCH3 2895.00
4 νOH 3450.40
5 νCH2 2590.00

IR SPECTRUM DATA OF Ni COMPLEX

TABLE 8

Sr.No GROUP ν Values (cm-1)

1 δ=C-H 2918.16
2 ν C=N 1616.60
3 ν M-O(Stretching) 421.35
4 ν M-N 515.82

IR SPECTRUM DATA OF Co COMPLEX

TABLE 9

Sr.No GROUP ν Values (cm-1)

1 δ=C-H 2919.52
2 ν C=N 1615.85
3 ν M-O(Stretching) 433.00
4 ν M-N 532.00

28
3.6 ULTRA VIOLET SPETROSCOPY

Procedure :
1. Prepare 30 ppm solutions of Schiff base and Complexes in DMSO.
2. Record reading for these solutions.

1.Conversion of λ in nm to cm-1 i.e. wave no.

E = hv

= hc = hc (1/λ )
λ

E = Energy
ν = frequency
h = Planks constant
c = velocity
λ = wavelength in nm or m
1/λ = wave .no in cm-1

υ = (1/ λ x 10-7 cm)

= (1x107) cm-1
λmax

Because of allow and forbidden transition in the range of 104 to105 mol/dm3
1. εmax = A
bc

A = Absorbance;
b = path length of cell (1 cm)
c = conc. of solution
c = ____(weight taken in g) mol dm-3
(mol. Weight of complex in g)

In general only the first spin allowed d-d transition may be observed, since these
are mostly marked by the high intensity charge transfer absorptions. The position of the

29
second d-d transitions band is often shifted very considerably by overlapping with the
charge transitions.
For the [C18H14NO] and [Ni(L)2Cl2] , [Co(L)2Cl.H2O] ions there are in general 3
bands towards the blue end of the visible region, which together with any additional
absorption in the blue end due to charge transfer transitions are responsible for the
characteristic Yellow, green and brown colours of Schiff base, Ni and Co complex
respectively.
Electronic absorption spectra of both the Schiff base and complexes were recorded
by preparing their solution in DMSO solvent. The original spectra are reproduced from
Fig. no. 4 to 6. The result of the electronic absorption spectra of [C18H14NO] and
[Ni(L)2Cl2] , [Co(L)2Cl.H2O] complexes are reported in Table no. 12 to 14.
[C18H14NO] show absorption bands at 21786.0cm-1, 22831.0cm-1 and 28208.0cm-
1
,. 31746.0 cm-1, 38986.0 cm-1, Similarly [Ni(L)2Cl2] complex exhibit three absorption
bands at 2421.0cm-1, 4566.0cm-1 and 3861.0cm-1. Similarly, [Co(L)2Cl.H2O] complex
exhibit three absorption bands at 22988.0 cm-1, 31446.0 cm-1 , 38610.0cm-1 , 42372.0 cm-1.
The strong absorption bands observed around 38986.0 cm-1 and 3861.0cm-1 and at 42372.0
cm-1.Schiff base and both complexes can be assigned to intra ligand л → л* and Charge
Transfer transitions respectively.
The absorption band observed at around 3861.0cm-1 and 42372.0 cm-1 in both the
complexes is assigned to M → L charge transfer transitions. The d-d bands are recovered
by the high intensity charge transfer bands. The UV spectra suggest that the energy states
of the л electron system of the ligand suffer substantial alternation on complexation. These
often obscure the two d-d bands found towards the blue end of the visible region
corresponding to the transition from A1g→T1g and 1T2g upper state.

30
 OBSERVATION TABLE

ULTRA -VIOLET TRANSITION FOR SCHIFF BASE

TABLE 10
Sr. λmax in Absorbance Conc. Path length Wave No. εmax Transition
No nm (mol/dm3) (cm) cm-1x104 (mol/dm3)
1 459.00 0.368 2.1786 31129.00 n→ π*
2 438.00 0.396 2.2831 33161.00 n→ π*
3 354.50 0.508 1.186x10-5 1 2.8208 54654.00 π → π*
4 315.00 0.654 3.1746 75666.00 π → π*
5 256.50 0.906 3.8986 11568.00 π → π*

Abs.
1.4

1.2

0.8
absorbance

0.6

0.4

0.2

0
200 300 400 500 600 700 800
wavelenth

Fig.4 UV SPECTRA OF SCHIFF BASE

31
Calculation:

1. υ = 1/ ( λ x 10-7)

= 1/ (460 x 10-7)

= 2.174 x 10-4 cm-1

2. c = 0.030
261.35
= 1.186 x 10-5 mol dm-3

3. ε = A
Bc

= __0.3698____
1 x 1.186x 10-5

= 3.1180x104 mol dm3

32
ULTRA -VIOLET TRANSITION FOR NICKEL COMPLEX

TABLE 11

Sr. λmax Abs. Conc. Path Wave No εmax Transition

No (nm) (mol/dm3) length cm-1x104 (mol/dm3)
(cm)
z3
1 410.00 0.749 1 2.42 92800.00 T1(F) → 3T2
(P)
2 317.00 0.755 8.29x10-6 1 4.56 93017.00 Charge Transfer

3 257.00 1.786 1 3.86 220786.00 Charge Transfer

1.8

1.6

1.4

1.2
Absorbance

0.8

0.6

0.4

0.2

0
200 300 400 500 600 700 800
Wavelenth

Fig.5 UV SPECTRA OF NICKEL COMPLEX

33
 ULTRA -VIOLET TRANSITION FOR COBALT COMPLEX

TABLE 12

Sr. λmax Abs. Conc. Path Wave no εmax Transition

No. (nm) (mol/dm3) length cm-1x104 (mol/dm3)
(cm)
1 435.00 0.275 8.034x10-6 1 2.2988 41474.00 4A2(F)→ 4T1(F)
2 318.00 0.344 8.034x10-6 1 3.1446 97192.00 4A2(F)→ 4T1(P)
3 259.00 0.329 8.034x10-6 1 3.8610 165477.00 Charge Transfer
4 236.00 0.808 8.034x10-6 1 4.2372 93939.00 Charge Transfer

Fig.6 UV SPECTRA OF COBALT COMPLEX

34
3.7 MASS SPECTROSCOPY
Reaction took place as follows ,

CH N CH3

OH
-OH
261m/z

CH N CH3

243m/z
-129 m/z
- C10H18

HC N CH3

115.08m/z
-24m/z
-CH=N

CH3

91.0 m/z

35
C:\Xcalibur\data\OCTOBER 2009\DG-5D 10/9/2009 3:37:32 PM

RT: 0.00 - 30.01

23.54 NL:
100 1.11E8
90 TIC MS
DG-5D
80

Relative Abundance 70

60

50

40

30

20
29.09 29.86
10 25.93 27.54
4.31 5.55 7.44 8.63 10.35 12.02 12.76 15.68 17.36 19.01 20.56 21.27
0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Time (min)

DG-5D #2747 RT: 23.54 AV: 1 NL: 4.04E7

T: + c Full ms [40.00-400.00]
260.00
100

90
80
Relative Abundance

70
260.90
60

50
40

30
20 244.10
261.89
10 115.08 217.09
65.04 91.03 129.71 170.03 205.09 262.84 295.44 326.78 342.73 376.80 391.70
0
50 100 150 200 250 300 350 400
m/z

Fig.7 MASS SPECTRA OF SCHIFF BASE

36
3.8 NMR SPECTROSCOPY

Complex : Schiff base

Molecular formula: 261.35mg

NMR VALUES FOR SCHIFF BASE

TABLE 13

Sr.No Group δ (ppm)

1 -OH 10.825
2 -CH=N 9.294
3 -CDCl3 7.363
4 - OCH3 3.409
5 -CH3 2.408

1
H NMR study of [C18H14NO]
The 1H NMR spectrum of [C18H14NO] shows aromatic protons between the range
of 5.96 – 6.98 ppm. The signal due to proton of HC=N group is observed at 9.294 ppm in
the ligand (L1). The signal appeared at 10.85 can be assigned to phenolic oxygen. The
signal appeared at 2.408 ppm is due to the hydrogen of methyl group and signal at the
3.409 ppm is due to the methoxy group.

37
Fig.8 NMR SPECTRA OF SCHIFF BASE

38
3.9 OBSERVATION OF TGA AND DTA

Thermal Decomposition Studies of Nickel (II) Complexe

The thermograms of the complexes were recorded to determine the thermal

stability and study the decomposition pattern of metal complexes. The rate of heating was
maintained at 10°C/min. from 25°C to 1000°C. The analysis was carried out in an inert
atmosphere by flushing nitrogen gas to eliminate formation of gaseous product. The TG
curve for [Ni(L)2Cl2] reproduced in Fig. no. 8 . The thermal stability of organometallic
compounds can be studied using thermogravimetry. These compounds are stable at room
temperature but they decompose or at least gain to decompose above 200°C. It becomes
necessary to establish the stability of Ni(II) complex against temperature variations.
Thermogravimetry (TG) curve for the Ni(II) complex is scanned in the range of 25°C to
1000°C. The percentage weight loss corresponding to increase in temperature is recorded
continuously.
The thermogram of Ni(II) complex of L1 shows that the complex starts
decomposing gradually till it attains the temperature corresponding to 500°C. After this
[Ni(L)2Cl2] shows sharp decrease in weight, indicating decomposition of complex.
Organic content of the metal complex is removed during this loss and decomposition
continues upto the temperature 500°C. The percentage weight loss of organic content from
the Ni(II) complex of L1 complex was found to be 80.52%. After this the weight of the
complex remains constant and the horizontal nature of the curve indicates the presence of
thermally stable residual metal oxide (NiO).

Reaction
[Ni(L2)Cl2] (NiO).
86.7%

Thermal Decomposition Studies of Cobalt (II) Complexe

The thermograms of the complexes were recorded to determine the thermal
stability and study the decomposition pattern of metal complexes. The rate of heating was
maintained at 10°C/min. from 25°C to 1000°C. The analysis was carried out in an inert
atmosphere by flushing nitrogen gas to eliminate formation of gaseous product. The TG
curve for [Co(L)2Cl.H2O] reproduced in Fig. no. 9. The thermal stability of organometallic

39
compounds can be studied using thermogravimetry. These compounds are stable at room
temperature but they decompose or at least gain to decompose above 200°C. It becomes
necessary to establish the stability of Co(II) complexes against temperature variations.
Thermogravimetry (TG) curves for the Co(II) complex is scanned in the range of 25°C to
1000°C. The percentage weight loss corresponding to increase in temperature is recorded
continuously.
The thermogram of Co(II) complex of L1 shows that the complex starts
decomposing gradually till it attains the temperature corresponding to 500°C. Till this
point weight corresponding to 1 mole of water per mole of Co(II) complex is removed.
The loss of water molecules in Co(II) complex is a single step process, indicated by
exothermic peak. The percentage weight loss corresponding to loss of water molecule
from thermogram was found to be 2.50%
After this [Co(L)2Cl.H2O] shows sharp decrease in weight, indicating
decomposition of complex. Organic content of the metal complex is removed during this
loss and decomposition continues upto the temperature 500°C. The percentage weight loss
of organic content from the Co(II) complex of L1 complex was found to be 90.77%. After
this the weight of the complex remains constant and the horizontal nature of the curve
indicates the presence of thermally stable residual metal oxide (CoO).
Reaction
[Co(L2)Cl.H2O] (CoO).
90.77%

40
Obsereved
% of metal oxide = 9.00%
% of organic matter = 86.70%
No water molecule is present in Ni complex
Calculated:
% of metal oxide = 8.09%
% of organic material = 85.54%

120

100

80
Weihgt loss

60

40

20

0
0 100 200 300 400 500 600 700 800 900 1000
Temperature

Fig.9 THERMAL DEGRADATION SPECTRA OF NICKEL COMPLEX

41
Thermal Decomposition Studies of Cobalt (II) Complexes
Obsereved
% of metal oxide = 7.02%
% of organic matter = 90.77%
% of water = 2.50%
Calculated:
% of metal oxide = 8.03%
% of organic material = 87.91%
% of water = 2.51%

120

100

80
Weight loss

60

40

20

0
0 200 400 600 800 1000 1200
Temperature

Fig.10 THERMAL DEGRADATION SPECTRA OF COBALT

42
 CHAPTER 4
APPLICATIONS OF SCHIFF BASES AND
THEIR METAL COMPLEXES.
_________________________________________
Schiff bases and its metal complexes have important applications in medical,
agricultural, analytical, biological and industrial field. They play a significant role in
several metabolic reactions, biological processes and organic syntheses. Schiff’s bases
prepared from semicarbazones and thiocarbazones possess a wide spectrum of medicinal
properties. It is also observed that this biological activity is often related to the chelating
ability of the metal ion. Numbers of metal chelates of the transition metals with sulphur
containing ligand have shown anticancer and anti-tumour activity16.
The Schiff base transitional metal complexes are used as inorganic polymers in
polymer industry17. Studies on Schiff bases and their transitional metal complexes have
caught the imaginations of researchers throughout the globe. Schiff base is now hot topic
in every research field specifically in basic Sciences. Schiff bases and metal complexes of
Schiff bases made their mark in every field for eg. Medicine, Dyes and pigments. Fossil
Fuels, Polymers and plasticizers, Agrochemicals, Catalysts, organic Coatings, Corrosion
Inhibitors, Liquid Crystals Organic synthesis, Essentials Oils and Cosmetics, Toxicology,
photography, Asymmetric Synthesis, Optical materials etc.,
(1) Pharmaceuticals :
(a) Schiff base – substituted phenols process for their preparation & their use in the
treatment of cell associated diseases eg. tumours, etc.
(b) Anticataract18pharmaceutical containing antioxidants.
A pharmaceutical for the prevention of cataract contains Sulphur containing Amino
acid, their derivatives or Schiff bases.
(2) Medicine:
It has been acknowledged that primary event in mammalian19,20 vision is a light-
initiated cis-to-trans isomerization of the retinal chromophore bond, via a protonated
Schiff base, to a lysine residue in the opsin apoprotein.

43
(3) Coatings:
Anticorrosive21 electrophoretic coatings composition contains aqueous Binders and
reaction products of Cinnamaldehyde with the amines R(CH2)nNH2 (R=alkyl, aryl,
NH2 ; n=0-10) was obtained as corrosion inhibitor.
(4) General Organic Chemistry:
(a) Michael22 addition promoted by bis-bidentate Ni(II) Schiff base complex derived
from aromatic 2-hydroxy aldehydes.
(b) Aza Cope23 rearrangement of Schiff bases derived from endo-Norbornen -5-
amines.
(5) Air Pollution and industrial Hygiene: Deodrants24 containing transition metal
complexes of Schiff bases for treating odorous air from refrigerators or raw garbage.
(6) Synthetic High Polymers: Preparation of magnetic Iron–Schiff bas polymer chelate
compounds (Mol. Wt. 4000–5000 Daltons) useful for recording applications and
magnetic films.
(7) Amino acids, peptides, Protein: Catalytic preparation of optically active amino acids
from Schiff bases by cobalt compounds, optically active tertiary phosphines and
reducing agents.
(8) Agrochemical:
(a) Pesticidal activity of arylidene -6-Aminoquinolines25.
Substituted aromatic Schiff bases proved to be most effective against Spider mite on
beans. Proved to be effective against Verticillium dahliae and Botrytiscincerea. These
Schiff bases even controlled powdery mildew of cucumbers and stem rust of wheat.
(9) Researches have made an attempt to utilize Schiff bases as an important tool for
separation & selection of trace amount of metal like Al3+ , Cr3, Fe3+, Ga3+, Ni2+, Cu2+,
etc., .
(10) Inman & Macpherson26 have synthesized a serious of coloured pigments
derived from Schiff bases, their pigments have good colour strength, solvents
resistance & can be used in organic polymers.
(11) The Schiff base transitional metal complexes are used as in organic polymers in
polymer industry37.
Photopolymerisation of reactive mesogenic Schiff bases & related Metallomesogens
have been carriedout & liquid crystal properties of the resulting Zn(II) complexes
acrylic monomers are reported38.

44
(12) Technetium complexes with Schiff bases & phosphate coordination have been used
in myocardial perfusion imaging development based on myocardial uptake & rapid
blood & liver clearance.
(13) Schiff bases derived from thiazole & its metal complexes show antitubercular,
hypotensive & hypothermic29 activities.
(14) Schiff base of N-salicyl –N, -thiobenzohydrazide exhibit antitumour activity30.

45
 SUMMARY
_______________________________________
The project reported includes into 5 chapters. Chapter 1 gives information on general
introduction to schiff base, and its mechanism and properties. Chapter 2 describes the
experimental techniques used, Chapter 3 involves synthesis methods where as Chapter
4 involves Application of schiff base and complexes. From above experiment it is seen
that Co and Ni Complex is having octahedral geometry as follow,

C N CH3
Cl
O
Ni
O
Cl
H3C N C

Ni COMPLEX
From all above analysis it is proved that Ni complex is having octahedral structure.

C N CH3
Cl
O
Co
O OH2
H3C N C

H
Co COMPLEX

From all above analysis it is proved that Co complex is having octahedral structure.

46
 REFERENCES
_________________________________________

1. Werner, A., Z. Inorg. Chem., 3, 267 (1843).

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

3. Van Vleck, J. H., The theory of Electric and Mag. Susceptibilities Oxford
University Press (1932).

4. Lourent, and Gerhart, Annalen., 76, 304 (1850).

5. Shift H., Ann. Suppl., 3, 343 (1864).

6. Brown G. H., “Techniques of chemistry”, volume (III) Photochromism, wiley

interscience New York, 569-632, (1971).

7. Cohen M. D., and Schmidt G. M., J. Phys. Chem., 66, 2442 (1962).

8. Cohen M. D., Hirsnberg Y. and Schmidth G. M., J. Chem. Soc., Vol. 77, 5820
(1955).

9. M.C. Carthy P. J., Hovey R. J., Ueno K. and Martell A. E., J. Chem. Soc.,
Vol. 77820 (1955) .

10. Saha N., and Mallick B. N., J. Indian Chem. Soc ., 54, 1008 (1977).

11. Cutler A.R., Arlene C.S. and Dolphin D., Inor. Chem ., 24(14), 2276 (1985).
12. Cutler A.R., Alleyne C.S., and Dolphin D., Inor. Chem ., 24(14), 2281 (1985).

13. Mondal N., Mitr S., Gramilich V., Ghodi S.O. and Malik K. M. A., Polydron,
20,135 (2001).

14. Text Book of Organic Chemistry.

15. Text Book of Analytical Chemistry.

16. Ali Akbar, M., and Livgstone , S.E., Coordination Chem. Rev., 133,101 (1947).

17. Frihant E. J., and Bailar J. C., Inorg, Nucl. Chem.24, 1205 (1962).

18. Elstner E.F., (Solvon Arzneimittel –ver-Triebs-Und Lizenzgesllchaft m.b.h),

German patent DE.3, 617, 71103 Dec (1987).

19. Kandorih., Shichida. Y., and Yohizawa T., Biochem ., 66, 1197 (2001).

20. Makanishi K., Chem. Pharma.Bull., 48(10) 1399 (2000).

47
 21. Philips E., and Braig A., (Ciba-Geigy A.G.), European Patent EP 410,925,
30 Jan 1991[CA 115 :138320d]

22. Batteghi C., Schionato A., Rosini C., and SalvandoriP., J. Mol. Catal., 63(2),
15(1990).

23. Gilchrist T. L., Gonsalves A.M.R.,and Phino e Melo T.V. D., Tel.Lett., 34(43),
6945 (1993).

24. Osaka Y., Natromi Y., and Uchikuga S., [Sogo Pharmaceutical Co., LTD ],
Japese Patent JP 01, 118, 515 (89,118,515) 11th May1989.

25. Haddok E., nd Hopwood W., British Patent GB 2, 078, 212, 06th JAN
1982[CA 96:1741W]

26. Iman K., and Macpherson ., I. Chem . 24, 1205 (1962).

27. Frihant E. J., and Bailar J. C., Inorg,Nucl. chem.24, 1205 (1962).

28. Marmion M. E., Woulte S.R. Neumann W.J., Nosco D. I. and deutsch E., nuclear
Med. biol., 26970755 (1990).

29. Kapoor R.P., Rastogi M. K., Khanna R., Gorg C.P., Indian I. Chem. 23B, 390
(1984).

30. David R. Williams, chem. Revi., 72, 30 , 203 (1972).

48