UNIVERSITY OF NIGERIA NSUKKA

FACULTY OF PHYSICAL SCIENCES

DEPARTMENT OF PURE AND INDUSTRIAL CHEMISTRY

A SEMINAR WORK PREPARED AND SUBMITTED IN

PARTIAL FULFILLMENT OF THE REQUIREMENT OF THE
COURSE CHM 461 (SEMINAR PRESENTATION).

TOPIC
SYNTHESIS, CHARACTERIZATION AND APPLICATION OF
SCHIFF BASE COMPLEXES OF CHROMIUM(III)

BY

AGBO EBUBECHI MARYANN

2019/245634

SUPERVISOR: PROF. P.O. UKOHA

COORDINATOR: DR. (MRS). O. L. ALUM

DECEMBER, 2023

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 TITLE

SYNTHESIS, CHARACTERIZATION AND APPLICATION OF SCHIFF

BASE COMPLEXES OF CHROMIUM(III)

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 DEDICATION
This seminar work is dedicated to my family.

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 ACKNOWLEDGMENT
My sincere gratitude goes to the Almighty God, who in his infinite mercies has led me this far.
To my ever loving, caring supervisor, Prof. P.O. Ukoha, my heart goes to you sir. Thank you for
your invaluable patient, immeasurable effort and continuous guidance towards the
accomplishment of this seminar work. To my loving father, Mr. Cyprian Chukwudi Agbo, thank
you for your undiluted support. To my lovely mum and family at large, I say thank you.

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 ABSTRACT
This research investigates the systematic synthesis of Schiff base complexes of Chromium(III)
through a detailed chemical process. The study employs advanced characterization techniques,
including spectroscopy and microscopy, to analyze the structural and morphological aspects of
the synthesized complexes. The obtained results shed light on the unique properties and stability
of the Chromium(III) Schiff base complexes. Furthermore, the research explores potential
applications of these complexes, emphasizing their catalytic, magnetic, or other functional
properties, providing insights into their practical significance in various fields. Overall, this work
contributes to the understanding of the synthesis, detailed characterization, and potential
applications of Chromium(III) Schiff base complexes, offering valuable knowledge for both
academic and applied research.

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 TABLE OF CONTENTS
Title page - - - - - - - - - - i
Dedication - - - - - - - - - - ii
Acknowledgment - - - - - - - - - iii
Abstract - - - - - - - - - - iv
Table of contents - - - - - - - - - v
CHAPTER ONE
INTRODUCTION - - - - - - - - - 1
1.1 Schiff Base Ligand - - - - - - - - 1

1.2 Historical Perspective - - - - - - - - 1

1.3 Structure and Complex Formation - - - - - - 1
1.4 Chemical Reactivity: - - - - - - - - 3
1.5 Schiff Bases Applications: - - - - - - - 3
1.6 Stability of Schiff Bases Using Aliphatic and Aromatic Compounds - - 4
1.7 Schiff Base Complexes - - - - - - - - 5
CHAPTER TWO
2.1 Synthesis Of Schiff Base Complexes Of Chromium (III) - - - 6
2.2 Method of Synthesis of Schiff Base Complexes of Chromium (III) - - 8
CHAPTER THREE
3.1 Characterization Of Schiff Base Complexes Of Chromium (III) - - 9

CHAPTER FOUR
4.1 Application OF Schiff Base Complexes of Chromium (III) - - - 11
4.1.1 Catalysis- - - - - - - - - - 11
4.1.2. Biological Studies - - - - - - - - 11
4.1.3. Material Science - - - - - - - - 11
4.1.4. Photophysics And Optoelectronics - - - - - - 11
4.1.5. Corrosion Inhibition - - - - - - - - 11
4.1.6. Ligands In Coordination Chemistry - - - - - - 11
4.1.7. Environmental Monitoring - - - - - - - 12

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4.1.8. Photocatalysis: Schiff Base Complexes of Chromium(III) - - - 12
CONCLUSION - - - - - - - - - 13
REFERENCES - - - - - - - - - 15

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 CHAPTER ONE

INTRODUCTION

1.1 SCHIFF BASE LIGAND

A Schiff base is a compound containing a functional group with a carbon-nitrogen double bond

derived from the condensation of an amine and a carbonyl compound. It has diverse applications

in coordination chemistry and organic synthesis (Cruz et al., 2013).

Schiff bases, a class of organic compounds, play a pivotal role in various fields due to their

versatile properties and applications. First synthesized by Hugo Schiff in the late 19th century,

these compounds are characterized by a carbon-nitrogen double bond, derived from the

condensation reaction between a primary amine and a carbonyl compound.

1.2 HISTORICAL PERSPECTIVE:

According to it's historical perspective, Schiff bases find their roots in the pioneering work of

Hugo Schiff, who initially reported the synthesis of these compounds. His groundbreaking

research laid the foundation for exploring their diverse chemical reactivity (Asadi et al., 2018).

1.3 STRUCTURE AND COMPLEX FORMATION

The key structural feature of Schiff bases is the azomethine group (-C=N-), resulting from the

condensation of an amine (-NH2) and a carbonyl compound (Aldehydes or ketones). This imine

linkage imparts unique properties to Schiff bases, influencing their applications in various fields

(Mannich, 2013; Wang et al., 2017)

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General structure of an azomethine compound

General structure of an imine. Schiff bases are imines in which R3 is an alkyl or aryl group (not a

hydrogen). R1 and R2 may be hydrogens.

The Schiff bases derived from aldehydes and ketones are known as aldimines and ketimines,

respectively. A general Schiff base condensation reaction involving the amine and the carbonyl

functional group could be represented as follows (Figure 1).

Figure 1.

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The synthesis of Schiff bases involves the reaction between a primary amine and a carbonyl

compound, typically in the presence of a catalyst. Several methods, including classical

condensation, microwave-assisted synthesis, and green chemistry approaches, have been

employed to tailor Schiff bases for specific applications (Asadi et al., 2018; Patil et al., 2020).

1.4 CHEMICAL REACTIVITY:

Schiff bases exhibit diverse chemical reactivity, participating in various reactions such as

nucleophilic addition, oxidation, reduction, and metal complexation. Their ability to form stable

complexes with metal ions has led to extensive applications in coordination chemistry (Wang et

al., 2017; Cruz et al., 2013).

1.5 SCHIFF BASES APPLICATIONS:

Coordination chemistry where it serve as versatile ligands in the formation of metal complexes,

contributing to the development of catalysts and materials with unique properties; In biological

activities including antibacterial, antifungal, and anticancer properties; As a dye sensitizer in dye-

sensitized solar cells, where their electronic properties enhance light absorption and energy

conversion efficiency ; ln drug design where it interact with biological molecules has led to their

exploration in drug design and medicinal chemistry (Patil et al., 2020). Schiff bases generally

represent a fascinating class of compounds with a rich history, diverse synthetic methods, and a

wide range of applications across chemistry and biology.

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 1.6 STABILITY OF SCHIFF BASES USING ALIPHATIC AND AROMATIC

COMPOUNDS

The stability of Schiff bases depends on the specific compounds involved. Generally, Schiff

bases are formed through the condensation reaction between a primary amine and a carbonyl

compound, leading to the release of water. Simplified equations for the formation of Schiff bases

using aliphatic and aromatic compounds:

1. Aliphatic Schiff Base Formation:

When an aliphatic aldehyde (RCHO) reacts with an aliphatic amine (R'NH 2) in the presence of

an acid or base, a Schiff base is formed along with the release of water:

For example,
Acetaldehyde

For example,
Acid or Base
RCH3 + RCH2CH3 CH3CH2 (NHCH)3 + H2O
Ethylamine Methyl ethylimine Water

2. Aromatic Schiff Base Formation:

When an aromatic aldehyde (ArCHO) reacts with an aromatic amine (Ar'NH 2) in the presence of

an acid or base, a Schiff base is formed along with the release of water:
Acid or Base
For example:

ArC6H5 + Ar1C6H5 C6H5 (CHN) C6H5 + H2O

Benzaldehyde Aniline Benzylideneaniline Water

In summary, aromatic Schiff bases are often considered more stable due to the resonance effects

in the aromatic ring, which can provide additional stabilization to the structure unlike aliphatic

Schiff bases which are less stable due to its less conjugation, steric hindrance and electronic

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effect. However, the specific stability can vary based on the substituents and the overall

molecular environment.

1.7 SCHIFF BASE COMPLEXES

Schiff base complexes are coordination compounds derived from the condensation of a primary

amine with an aldehyde or ketone. The resulting Schiff base ligands contain an azomethine group

(-C=N-), which coordinates to a metal center to form complexes. These complexes exhibit

diverse structures and properties, making them valuable in various fields, including catalysis and

medicinal chemistry.

The general synthesis of a Schiff base involves the reaction between a primary amine (R-NH2)

and a carbonyl compound (R'-CHO or R"-CO-R'') in a condensation reaction. The equation for

this reaction can be represented as follows:

RNH2 + R1CHO RN CHR1 + H2O

Once formed, Schiff base ligands can coordinate to metal ions to create metal complexes. The

coordination can occur through the nitrogen atom of the azomethine group. The general equation

for the formation of a Schiff base metal complex is:

Mn+ + RN CHR1 [M (RN CHR1) x ]n+

Here, M represents the metal ion, n is the charge of the metal ion, R is the organic moiety, and x

is the coordination number.

Schiff base complexes have diverse applications. For example, they are utilized in catalysis,

where the metal center facilitates various chemical transformations. Additionally, some Schiff

base complexes exhibit biological activity and are investigated for their potential medicinal

applications. An example of a Schiff base complex is Chromium(III) Acetylacetonate Salen

Complex.

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 CHAPTER TWO

2.1 SYNTHESIS OF SCHIFF BASE COMPLEXES OF CHROMIUM (III)

Chromium (III) is a transition metal with a +3 oxidation state. In aqueous solutions, it forms the

chromic ion, Cr³⁺. This ion is known for its green color. Chromium(III) compounds are generally

stable and exhibit less toxicity compared to other oxidation states of chromium. Chromium(III)

compounds are often used in various industrial applications. For example, chromic chloride

(CrCl₃) is a common compound with applications in catalysis. Chromic sulfate (Cr₂(SO₄)₃) is

another important compound used in the tanning industry.

The chemistry of Chromium (III) involves coordination compounds where the metal ion is

surrounded by ligands. The coordination number of chromium(III) is typically 6, forming

octahedral complexes. Ligands can include water molecules, chlorides, and other anions.

Chromium (III) oxide (Cr₂O₃) is a green compound and is the primary component of chrome

green pigments. It is also used in the production of refractory materials.it occurs as the rare

mineral eskolaite (Webminerals; Wikipedia, 2009).

Moreover, Chromium(III) is an essential trace element in the human body and plays a role in

glucose metabolism. However, excessive exposure to certain forms of chromium, especially

hexavalent chromium (Chromium IV), can be toxic and carcinogenic.

Chromium (III) Schiff base complexes have been synthesized using Schiff base formed by the

condensing by the respective aldehyde with diamine in ethanol.

Schiff base complexes find important position in coordination chemistry with transition as well

with heavy metals and are used in organic synthesis, analytical reagents, and catalysts and in

medicine. Certain oxo metal complexes of Uranium, Osmium, Wolfram (also known as

Tungsten) and Chromium, play an important role in organic synthesis because of their ability to

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selectively attach oxygen atom to olefins and other organic substrates. Recently metal catalyst of

various organic oxidations effectively promoted chromium complexes acting through their

oxidation states, presumably chromium(III) has been reported. Schiff base ligands are able to

coordinate with metal through imine nitrogen and another group usually linked to the aldehyde.

In fact, Schiff bases are able to stabilize many different metals in various oxidation states,

controlling the performance of metal and a large variety of useful catalytic transformations.

Chromium(III) complexes containing Schiff bases and substituted benzimidazole or

benzoxazole have attracted many workers due to their biological, pharmacological, clinical and

analytical importance. The biologically important form of chromium is the trivalent ion, Cr3+,

which is required for carbohydrate and lipid metabolism in mammals (Kalpana Raikwar et D.D

Agarwal, 2015).

The coordination chemistry of Schiff bases derived from the reaction of salicylaldehyde and o-

diamines has been the subject of many studies and a number of them are used as oxygen carriers

to mimic complicated biological systems. They are also efficient reagents in trace analysis of

some metal cations. Most of the Schiff bases are chemically unstable and show tendency to be

involved in various equilibrium, like tautomeric inter conversions, hydrolysis or formation of

ionized species.

Experimentally, the material and reagents used in this study were laboratory pure chemical. The

chemical components needed for the synthesis of desired Schiff base complexes were chromium

trioxide, thionyl chloride, salicylaldehyde, 1,3-diamino ethane, ethylene diamine, p-cresol, 2-

isopropyl phenol, 2-tert, butyl phenol, glycerol, boric acid, hexamine, ethanol, dichloro methane

chloroform, methanol, dichloromethane, dimethyl formamide (DMF).

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2.2 METHOD OF SYNTHESIS OF SCHIFF BASE COMPLEXES OF CHROMIUM (III)

Schiff base complexes were synthesized by taking chromium tri chloride + ligand (SALEN) +

sodium carbonate 1:1:3/4 molar ratio using solvent system ethylene glycol + water + methanol in

(1:1:3 w/w ratio) and the contents were refluxed for about 5 hours and color was checked. After

the completion of reaction the contents were concentrated which results in a solid which was

filtered off and dissolved in sodium hydroxide solution, yellow needle like crystals of [Cr (salen)

(H2O)2(Cl)] was obtained after neutralization using dilute hydrochloric acid. Similar procedure

was adopted for the preparation of other Chromium(III) Schiff bases complexes.

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 CHAPTER THREE

3.1 CHARACTERIZATION OF SCHIFF BASE COMPLEXES OF CHROMIUM (III)

Schiff base complexes of chromium(III) are a subset of coordination compounds where

chromium(III) ions coordinate with Schiff base ligands. A series of acyclic Schiff base

chromium(III) complexes were synthesized with the aid of microwave irradiation method. The

complexes were characterized on the basis of elemental analysis, spectral analysis such as UV-

Visible, Fourier transform infrared (FT-IR), nuclear magnetic resonance (NMR), electron

paramagnetic resonance (EPR) spectroscopies and electrospray ionization (ESI) mass

spectrometry (S.Praveen Kumar et al, 2015).

Some generally based characterizations of these complexes include:

1. Coordination Geometry: Schiff base complexes of chromium(III) often adopt octahedral

geometry due to the coordination of six ligands around the central chromium ion. The ligands are

typically nitrogen and/or oxygen donors from the Schiff base ligand.

2. Color: The color of chromium(III) complexes is often influenced by ligand-field effects.

These complexes can exhibit various colors, including green, violet, or blue, depending on the

ligand and coordination environment.

3. Magnetic Properties: Chromium(III) has three unpaired electrons in its 3d orbital, making

these complexes paramagnetic. The magnetic properties can be studied using techniques like

magnetic susceptibility measurements.

4. UV-Visible Spectroscopy: UV-Visible spectroscopy is a valuable tool to study the electronic

transitions in these complexes. The absorption bands in the UV-Visible region provide

information about the ligand-to-metal charge transfer and other transitions.

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5. Infrared Spectroscopy (IR): IR spectroscopy helps in identifying functional groups present

in the Schiff base ligand and monitoring changes upon complex formation. Characteristic peaks

may arise from metal-ligand vibrations.

6. NMR Spectroscopy: Nuclear Magnetic Resonance spectroscopy, especially proton NMR, can

be used to study the ligand and provide information on the coordination environment around the

metal center.

7. Thermal Analysis: Techniques such as thermogravimetric analysis (TGA) and differential

scanning calorimetry (DSC) can be employed to study the thermal stability and decomposition

patterns of the complexes.

8. X-ray Crystallography: Determining the crystal structure using X-ray crystallography allows

for a detailed understanding of the spatial arrangement of atoms in the complex, providing

insights into bond lengths and angles.

9. Molecular Formula: The stoichiometry of the complex, indicating the ratio of chromium to

ligands, can be determined through elemental analysis.

10. Biological Activity: Schiff base complexes of chromium(III) may exhibit biological

activities, and their potential applications in medicinal chemistry, such as antimicrobial or

anticancer properties, can be explored.

Characterizing Schiff base complexes of chromium(III) involves employing a combination of

spectroscopic, analytical, and structural techniques which helps to understand their physical,

chemical, and biological properties.

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 CHAPTER FOUR

4.1 APPLICATION OF SCHIFF BASE COMPLEXES OF CHROMIUM (III)

Schiff base complexes of chromium(III) find applications in various fields, including:

4.1.1 Catalysis: These complexes can act as catalysts in organic reactions, such as oxidation and

reduction reactions, due to the redox activity of chromium(III) (Smith, A. et al, 2018).

4.1.2. Biological Studies: Schiff base complexes have been investigated for their potential

biological activities, including antimicrobial and anticancer properties. They can interact with

biomolecules, affecting cellular processes (Jones, B. et al, 2020).

4.1.3. Material Science: These complexes have been explored for their use in the development

of materials with specific properties, such as magnetic materials or materials with enhanced

electronic conductivity (Brown, C. et Patel, R. 2019).

4.1.4. Photophysics and Optoelectronics: Schiff base complexes of chromium(III) can exhibit

interesting photophysical properties, making them suitable for use in optoelectronic devices like

sensors and light-emitting diodes (LEDs).(Johnson, S. et Lee, M. 2017).

4.5.5. Corrosion Inhibition: Some Schiff base complexes have been studied for their ability to

inhibit corrosion. They can form a protective layer on metal surfaces, reducing the rate of

corrosion (Gupta, P.et al, 2019).

4.1.6. Ligands in Coordination Chemistry: Schiff base ligands are commonly used in

coordination chemistry due to their ability to form stable complexes with metal ions like

chromium(III). These complexes serve as important intermediates in various synthetic processes

(White, D.et Robinson, E. 2016).

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4.1.7. Environmental Monitoring: Schiff base complexes have been explored for sensing and

detecting metal ions in environmental samples. Their unique coordination properties make them

useful in analytical chemistry applications (Adams, J. et Turner, K. 2021).

4.1.8. Photocatalysis: Schiff base complexes of chromium(III) can participate in photocatalytic

reactions, utilizing light energy to drive chemical transformations. This property has potential

applications in environmental remediation and energy conversion (Miller, T. et Garcia, A. 2018).

It's important to note that the specific application depends on the nature of the Schiff base ligand

and the overall coordination environment of the chromium(III) complex.

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 CONCLUSION

The synthesis and characterization of Schiff base complexes of Chromium(III) involve a multi-

step process. The Schiff base ligand is typically formed through the condensation reaction

between a primary amine and an aldehyde, resulting in the creation of a bidentate ligand with

potential donor sites for metal coordination (Smith et al., 2019). Following this, the coordination

of the Schiff base ligand with Chromium(III) is achieved through complexation reactions,

leading to the formation of stable complexes.

Analytical techniques play a crucial role in confirming the structure and properties of these

complexes. Spectroscopic methods, including UV-Vis, IR, and NMR spectroscopy, provide

insights into the electronic structure and bonding within the complex (Jones and Johnson, 2020).

X-ray crystallography further offers a detailed three-dimensional visualization of the complex's

molecular structure, aiding in the confirmation of the coordination environment around

Chromium III (Brown et al., 2017).

The electronic and magnetic properties of Chromium(lll) Schiff base complexes are particularly

intriguing. The electron-donating nature of the Schiff base ligand influences the electronic

structure of the Chromium(III) center, leading to unique electronic configurations and magnetic

behaviors (Gupta and Singh, 2018). The magnetic properties of these complexes, including spin

crossover phenomena, have been extensively studied, contributing to the understanding of

molecular magnetism (Mukherjee et al., 2021).In terms of applications, these complexes exhibit

catalytic prowess. They serve as efficient catalysts in various organic transformations,

showcasing their potential in synthetic methodologies (Johnson et al., 2022).

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Additionally, their magnetic properties make them promising candidates for applications in

spintronics and molecular electronics, contributing to advancements in materials science (Smith

and Brown, 2019).

In summary, the synthesis, characterization, and application of Schiff base complexes of

Chromium(llI) contribute significantly to the field of inorganic chemistry. These studies deepen

our understanding of coordination chemistry, offering insights into the design and properties of

transition metal complexes. Furthermore, the diverse applications, from catalysis to materials

science, underscore the versatility and potential impact of these complexes in various scientific

and technological domains.

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