CHAPTER TITLE Pg.

No

1 ABSTRACT 5
INTRODUCTION
6
2.1 DEFINITION AND IMPORTANCE OF
2 COORDINATION COMPOUNDS 9
2.2 HISTORICAL DEVELOPMENT
2.3 SCOPE AND APPLICATIONS
BASIC CONCEPTS AND TERMINOLOGY
3.1 LIGANDS 12
3 3.2 COORDINATION NUMBER 14
3.3 CHELATION 17
3.4 TYPES OF COORDINATION COMPOUNDS
STRUCTURE AND BONDING IN COORDINATION
COMPOUNDS 20
4.1 THEORY OF COORDINATION BONDS 21
4
4.2 VALENCE BOND THEORY 23
4.3 CRYSTAL FIELD THEORY 25
4.4 LIGAND FIELD THEORY
CLASSIFICATION OF COORDINATION
COMPOUNDS 27
5 5.1 BASED ON COORDINATION NUMBER 28
5.2 BASED ON THE TYPE OF LIGANDS 30
5.3 BASED ON THE GEOMETRY OF THE COMPLEX
PREPARATION AND SYNTHESIS OF
COORDINATION COMPOUNDS 33
6 6.1 METHODS OF SYNTHESIS 35
6.2 EXAMPLES OF SYNTHESIS 37
6.3 CHALLENGES IN SYNTHESIS
REACTIVITY AND STABILITY OF COORDINATION
COMPOUNDS 40
7 7.1 SUBSTITUTION REACTIONS 42
7.2 REDOX REACTIONS
7.3 FACTORS AFFECTING STABILITY
APPLICATIONS OF COORDINATION COMPOUNDS 46
8.1 IN BIOLOGY 47
8 8.2 IN INDUSTRIAL CHEMISTRY
8.3 IN ENVIRONMENTAL CHEMISTRY
8.4 IN MEDICINE
CASE STUDIES OF IMPORTANT COORDINATION
9 COMPLEXES
9.1 HEMOGLOBIN AND MYOGLOBIN
TABLE OF CONTENT

4
 TABLE OF CONTENT Cont..

CHAPTER TITLE Pg.No

5
CONCLUSION
9

10 BIBLOGRAPHY

5
 ABSTRACT

Coordination compounds are chemical complexes consisting of a central metal atom or ion
bonded to surrounding ligands. These compounds exhibit unique properties due to the
interactions between the metal and ligands, and are essential in various fields like chemistry,
biology, and industry. This thesis explores the fundamental concepts of coordination
chemistry, including ligands, coordination numbers, and types of complexes. It examines the
historical development of the field, particularly Alfred Werner's contributions to coordination
theory. The thesis delves into key bonding theories, such as Valence Bond Theory (VBT),
Crystal Field Theory (CFT), and Ligand Field Theory (LFT), which explain the electronic
structure and reactivity of these compounds. Synthesis methods, including direct synthesis
and solvothermal techniques, are discussed alongside the reactivity of coordination
compounds in substitution and redox reactions. Case studies highlight their applications in
medicine, biology, industry, and environmental chemistry. The thesis concludes by
addressing future challenges and potential advancements in coordination chemistry.

6
 INTRODUCTION

2.1 DEFINITION AND IMPORTANCE OF COORDINATION COMPOUNDS

Coordination compounds, or complexes, are chemical compounds that consist of a central

metal atom or ion bonded to a surrounding array of ligands. These compounds are
characterized by the ability of the metal center to form coordinate covalent bonds with
ligands, leading to distinct chemical properties. Coordination compounds have applications in
many fields, including materials science, catalysis, medicine, and environmental science.

Coordination chemistry is crucial for understanding the behavior of transition metals, which
often form highly stable complexes with various ligands. The role of coordination
compounds in biological systems (e.g., hemoglobin and enzymes) further highlights their
importance.

2.2 HISTORICAL DEVELOPMENT

The concept of coordination compounds dates back to the early 19th century. Early studies by
scientists like Berzelius and Wöhler established the idea that certain metal ions could form
stable compounds with ligands. However, it wasn’t until the work of Alfred Werner in the
late 19th century that coordination chemistry began to take shape in its modern form.
Werner’s theories on coordination bonds and octahedral geometry of metal complexes
revolutionized our understanding of metal-ligand interactions.

Early Observations (18th–19th Century):

1. Discovery of Prussian Blue (1704)

o One of the first known coordination compounds, Prussian Blue
(Fe₄[Fe(CN)₆]₃), was synthesized and used as a pigment.
2. Berzelius's Contributions (1812–1820)
o Swedish chemist Jöns Jacob Berzelius classified compounds into organic and
inorganic categories and noted the peculiar nature of "complex" compounds.

Development of Bonding Theories (20th Century):

1. Valence Bond Theory (VBT) – 1930s

o Linus Pauling explained the bonding in coordination compounds using
hybridization of orbitals.

2. Crystal Field Theory (CFT) – 1940s

o Introduced by Hans Bethe and John Hasbrouck van Vleck to describe the
electronic structure and color of complexes.

3. Ligand Field Theory (LFT) – 1950s

o Combined aspects of CFT and molecular orbital theory to provide a more
comprehensive understanding.

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2.3 SCOPE AND APPLICATIONS

Coordination compounds are not only a subject of academic interest but have wide-ranging
applications. In materials science, they are used in creating novel catalysts and conducting
materials. Coordination chemistry also plays a vital role in biochemistry, where many
biological molecules, such as enzymes, are coordination compounds of metal ions.
In medicine, coordination complexes such as cisplatin are critical in cancer treatment.
The environmental applications of these compounds are also significant in terms of
pollution control and remediation.

Applications and Modern Innovations (21st Century)

 Coordination compounds found applications in medicine (e.g., Cisplatin for cancer

therapy), industry (catalysis), and biochemistry (metalloenzymes).
 Research continues into bioinorganic complexes, supramolecular chemistry, and
environmental applications.

Medicine

 Cancer Treatment:
o Cisplatin ([Pt(NH₃)₂Cl₂]) is a widely used chemotherapy drug for treating
various cancers.
o Other platinum-based compounds like carboplatin and oxaliplatin are also
effective.

 Imaging and Diagnostics:

o Gadolinium complexes are used as contrast agents in Magnetic Resonance
Imaging (MRI).
o Technetium-99m complexes are applied in radiopharmaceutical imaging.

 Antimicrobial and Antiviral Agents:

o Metal coordination complexes show promise as antibiotics and antiviral
agents.

Industrial Catalysis

 Homogeneous Catalysis:
o Wilkinson's catalyst ([RhCl(PPh₃)₃]) is used in hydrogenation reactions.
o Ziegler–Natta catalysts, involving titanium and aluminum complexes, are
essential for polymerizing alkenes like polyethylene and polypropylene.

 Electrochemical Applications:
o Metal-phthalocyanine complexes are used in fuel cells and batteries.

Biological Systems

 Metalloenzymes:

8
 o Coordination compounds like heme (Fe²⁺-porphyrin) and vitamin B12 (Co³ ⁺
complex) are crucial in biological processes such as oxygen transport and
enzymatic reactions.

 Photosynthesis:
o Chlorophyll, a magnesium coordination compound, is central to
photosynthesis.

 Therapeutic Uses:
o Chelation therapy with EDTA is used for treating heavy metal poisoning.

Environmental Chemistry

 Water Treatment:
o Coordination complexes of iron and manganese catalyze the removal of
contaminants in water.

 Carbon Capture:
o Transition metal complexes are investigated for their ability to capture and
convert CO₂.

Analytical Chemistry

 Colorimetric Analysis:
o Complexes like Fe(SCN)₆³⁻ are used in qualitative and quantitative analysis
due to their intense colors.

 Detection of Metal Ions:

o Ligand-based sensors help detect toxic metal ions like mercury or lead in
environmental samples.

Agriculture

 Micronutrient Supply:
o Chelated compounds like Fe-EDTA and Zn-EDTA are used as fertilizers to
supply essential micronutrients to plants.

 Pesticides:
o Metal complexes are studied for their potential as effective pest control agents.

Material Science

 Magnetic and Optical Materials:

o Lanthanide complexes are used in lasers, phosphorescent materials, and LEDs.

9
 o Spin-crossover coordination compounds are studied for use in memory
devices.

 Coordination Polymers:
o Metal-organic frameworks (MOFs) are utilized for gas storage, separation, and
catalysis.

Supramolecular Chemistry

 Coordination compounds serve as building blocks for supramolecular architectures,

enabling applications in nanotechnology and drug delivery systems Top of Form

BASIC CONCEPTS AND TERMINOLOGY

3.1 LIGANDS

Ligands are atoms, ions, or molecules that donate electron pairs to the central metal atom to
form coordinate covalent bonds. Ligands are classified based on the number of electron pairs
they donate:

 Monodentate Ligands: Ligands that donate one pair of electrons (e.g., Cl ⁻, NH₃,
H₂O).
 Bidentate Ligands: Ligands that donate two pairs of electrons (e.g., ethylenediamine,
oxalate).
 Polydentate Ligands: Ligands that donate more than two pairs of electrons (e.g.,
EDTA, DTPA).

Based on Denticity (Number of Donor Atoms)

1. Monodentate Ligands (Unidentate)

o Ligands that donate a single electron pair to the metal center.
o Examples:
 Neutral: NH₃, H₂O
 Anionic: Cl⁻, OH⁻, CN⁻

2. Bidentate Ligands
o Ligands that have two donor atoms and can bind at two sites.
o Examples:
 Ethylenediamine (en), C₂O₄²⁻ (oxalate)

3. Polydentate Ligands
o Ligands with multiple donor atoms.

10
 o Examples:
 Tridentate: Diethylenetriamine (dien)
 Hexadentate: Ethylenediaminetetraacetate (EDTA⁴⁻)

Based on Charge

1. Neutral Ligands
o Ligands with no overall charge.
o Examples: CO, NH₃, H₂O

2. Anionic Ligands
o Ligands with a negative charge.
o Examples: Cl⁻, NO₃⁻, OH⁻, CN⁻

3. Cationic Ligands
o Ligands with a positive charge (rare).
o Example: NO⁺ (Nitrosonium)

Based on Nature of Bonding

1. Sigma (σ)-Donor Ligands

o Donate electron density through a single sigma bond.
o Examples: NH₃, H₂O, Cl⁻

2. Pi (π)-Acceptor Ligands
o Accept electron density from the metal's d-orbitals via π-back bonding.
o Examples: CO, NO, C₂H₄

3. Mixed Sigma and Pi Donors

o Ligands that exhibit both σ-donation and π-acceptance.
o Examples: CN⁻, SCN⁻

Special Classes of Ligands

1. Chelating Ligands
o Form rings with the metal ion, increasing stability.
o Examples: EDTA⁴⁻, oxalate (C₂O₄²⁻)

2. Ambidentate Ligands
o Ligands that can bind through more than one atom but use only one at a time.
o Examples: NO₂⁻ (Nitro/Nitrito), SCN⁻ (Thiocyanato/Isothiocyanato)

3. Flexidentate Ligands
o Polydentate ligands that can bind in multiple ways depending on coordination
environment.
o Example: EDTA (acts as hexadentate or tetradentate depending on the metal
center)

4. Macrocyclic Ligands

11
 o Large ring structures that form stable complexes.
o Examples: Porphyrins, Crown ethers

Based on Type of Atom Donating Electrons

1. Carbon Ligands
o Examples: CO, C₆H₆ (benzene), CH₃⁻

2. Nitrogen Ligands
o Examples: NH₃, NO₂⁻, pyridine (C₅H₅N)

3. Oxygen Ligands
o Examples: H₂O, OH⁻, O²⁻

4. Sulfur Ligands
o Examples: H₂S, SCN⁻, S²⁻

5. Phosphorus Ligands
o Examples: PH₃, P(C₆H₅)₃ (triphenylphosphine)

The nature and size of ligands influence the stability, geometry, and reactivity of the
coordination complex.

3.2 COORDINATION NUMBER

The coordination number refers to the number of ligand atoms directly bonded to the central
metal ion. It is influenced by the metal’s size, charge, and electronic configuration, as well as
the size and charge of the ligands. For example:

 A coordination number of 2 often results in a linear geometry (e.g., [Ag(NH₃)₂]⁺).

 A coordination number of 4 often leads to either a tetrahedral or square planar
geometry (e.g., [CuCl₄]²⁻).
 A coordination number of 6 typically leads to an octahedral geometry (e.g.,
[Fe(CO)₆]).

3.3 CHELATION

Chelation is the process by which a ligand binds to a metal ion at multiple sites, forming a
ring-like structure. Chelating ligands tend to form more stable complexes than monodentate
ligands due to the chelate effect, which increases the overall stability of the complex.

12
  Example: EDTA is a hexadentate ligand that can form multiple bonds with a metal
ion, stabilizing the coordination complex significantly.

Mechanism of Chelation

1. Chelating Ligands
o These are polydentate ligands with multiple donor atoms capable of binding to
a metal ion simultaneously.
o Examples:
 Ethylenediamine (en): A bidentate ligand with two nitrogen donor
atoms.
 Ethylenediaminetetraacetate (EDTA): A hexadentate ligand that can
bind via six donor atoms (four oxygen and two nitrogen).

2. Formation of Chelates
o Chelates form when a chelating ligand coordinates to a metal center, creating
one or more rings.
o Example: The complex of Ni²⁺ with ethylenediamine forms a five-membered
ring structure.

Stability of Chelates

Chelates are significantly more stable than complexes formed by equivalent monodentate
ligands. This phenomenon is known as the Chelate Effect.

13
Chelate Effect

 Entropy: The formation of a chelate releases more water molecules from the
hydration sphere of the metal ion, increasing entropy and stabilizing the complex.
 Ring Strain: Chelates with five- or six-membered rings are particularly stable due to
minimal ring strain.

Factors Affecting Chelation

1. Size of the Chelating Ligand:

o Larger ligands may form complexes with larger rings, which may have lower
stability due to ring strain.

2. Nature of the Metal Ion:

o Transition metals with higher charges and smaller ionic radii form more stable
chelates.

3. Ligand Denticity:
o Ligands with more donor atoms generally form more stable chelates (e.g.,
EDTA is more stable than ethylenediamine).

4. Steric and Electronic Effects:

o Bulky substituents or electronic factors may hinder chelation or influence
stability.

Applications of Chelation

Medicine

 Chelation Therapy:
o EDTA is used to treat heavy metal poisoning (e.g., lead, mercury) by forming
stable chelates that can be excreted.
o Desferrioxamine is used for iron overload in thalassemia patients.

 Pharmaceuticals:
o Chelates like Cisplatin target cancer cells.
o Gadolinium chelates are used as contrast agents in MRI imaging.

Biological Systems

 Metalloenzymes:
o Chelates like heme (iron-porphyrin complex) and chlorophyll (magnesium-
porphyrin complex) are vital for oxygen transport and photosynthesis.

 Chelating Agents in Nutrition:

o Chelated minerals (e.g., iron glycinate) are used in supplements for better
absorption.

14
Industrial Applications

 Catalysis:
o Chelating ligands like bipyridine and phosphines are used in metal-catalyzed
reactions.
o Ziegler–Natta catalysts utilize chelation for polymer production.

 Cleaning Agents:
o Chelating agents like EDTA and citrate are used in detergents to bind calcium
and magnesium ions, preventing hard water scaling.

Agriculture

 Micronutrient Delivery:
o Chelated fertilizers (e.g., Fe-EDTA) enhance nutrient availability to plants.

Environmental Chemistry

 Water Treatment:
o Chelating agents remove heavy metals and other contaminants from
wastewater.

Examples of Chelation

1. Ni(EDTA) Complex:
o [Ni(EDTA)]²⁻, where EDTA binds via six donor atoms, forming a highly
stable hexadentate complex.

2. Hemoglobin:
o Iron is chelated by a porphyrin ring in the heme group, facilitating oxygen
transport in blood.

15
 3. Cisplatin:
o The anticancer drug forms chelates with DNA, inhibiting cell replication.
o

3.4 TYPES OF COORDINATION COMPOUNDS

Coordination compounds can be classified based on the number and types of ligands
involved, their coordination number, and their geometric arrangement.

 Mononuclear vs. Polynuclear Complexes: Mononuclear complexes have a single

metal ion at the center, while polynuclear complexes contain two or more metal ions.
 Cationic, Anionic, and Neutral Complexes: Depending on the charge on the metal-
ligand complex, coordination compounds can be cationic (positively charged), anionic
(negatively charged), or neutral.
 Homoleptic vs. Heteroleptic Complexes: Homoleptic complexes consist of only one
type of ligand, while heteroleptic complexes have more than one type of ligand.

Based on Charge of the Complex

1.1. Cationic Complexes

 Complexes carrying a net positive charge.

 Example: [Co(NH3)6]3+[Co(NH3)6]3+ (hexaamminecobalt(III))
 Applications: Often used in catalysis and as intermediates in synthetic reactions.

1.2. Anionic Complexes

 Complexes with a net negative charge.

 Example: [Fe(CN)6]4−[Fe(CN)6]4− (hexacyanoferrate(II))
 Applications: Used in electroplating and as reagents in analytical chemistry.

1.3. Neutral Complexes

 Complexes that are electrically neutral.

 Example: [Ni(CO)4][Ni(CO)4] (tetracarbonyl nickel(0))
 Applications: Industrial catalysts and reagents in organic synthesis.

Based on Bonding

16
Werner-Type Complexes

 Traditional complexes with primary (ionic) and secondary (coordination) valencies.

 Example: [Co(NH3)6]Cl3[Co(NH3)6]Cl3
 Historical Significance: Pioneered by Alfred Werner, foundational in coordination
chemistry.

Organometallic Complexes

 Contain metal-carbon bonds, typically to organic ligands.

 Example: [Fe(C5H5)2][Fe(C5H5)2] (ferrocene)
 Applications: Catalysis, pharmaceuticals, and material science.

Bioinorganic Complexes

 Contain metals essential for biological processes.

 Example: Hemoglobin (iron-porphyrin complex)
 Applications: Oxygen transport, enzymatic reactions.

STRUCTURE AND BONDING IN COORDINATION COMPOUNDS

17
4.1 THEORIES OF COORDINATION BONDING

Coordination compounds are described using various bonding models, each providing insight
into the nature of metal-ligand interactions. Three of the most important theories are:

 Valence Bond Theory (VBT), which explains the bonding as the result of orbital
overlap between the metal and ligand.
 Crystal Field Theory (CFT), which explains the electronic structure of the complex
based on electrostatic interactions.
 Ligand Field Theory (LFT), an extension of CFT that incorporates molecular orbital
theory for a more comprehensive description.

Werner’s Coordination Theory (1893)

Pioneer: Alfred Werner

Key Features:

 Distinguished between primary valency (oxidation state of the metal) and secondary
valency (coordination number).
 Proposed the octahedral structure for complexes like [Co(NH3)6]Cl3[Co(NH3)6]Cl3.

Limitations:

 Did not explain the nature of the bond between the metal and ligands.

Valence Bond Theory (VBT)

Key Features:

 Bond formation occurs via the overlap of metal’s hybridized orbitals with ligand
orbitals.
 Hybridization types determine the geometry:
o sp³: Tetrahedral (e.g., [NiCl4]2−[NiCl4]2−)
o d²sp³: Octahedral (e.g., [Co(NH3)6]3+[Co(NH3)6]3+)

Strengths:

 Explains geometries and magnetic properties of complexes.

Limitations:

 Fails to explain color and spectral properties.

 Cannot account for weak and strong field ligands effectively.

Crystal Field Theory (CFT)

18
Key Features:

 Ligands are treated as point charges, and their interaction with the metal ion's d-
orbitals splits the d-orbitals into different energy levels.
 The energy difference (ΔΔ) between the split d-orbitals depends on the ligand's field
strength.

Key Concepts:

 Octahedral Field: Splits d-orbitals into t2gt2g (lower energy) and egeg (higher
energy).
 Tetrahedral Field: Splits d-orbitals oppositely, with ee (lower) and t2t2 (higher
energy).

Applications:

 Explains the color, magnetism, and stability of complexes.

 High-spin vs. low-spin complexes depend on the ligand's strength (e.g., weak-field
ligands like H2OH2O lead to high-spin, strong-field ligands like CN−CN− lead to
low-spin).

Limitations:

 Treats ligands as point charges, ignoring covalent bonding.

 Cannot explain spectral properties fully.

Ligand Field Theory (LFT)

Key Features:

 A refinement of CFT incorporating covalent character in metal-ligand bonds.

19
  Combines the concepts of molecular orbital theory with crystal field splitting.

Applications:

 Explains complex stability, spectroscopic properties, and magnetic behavior more

comprehensively than CFT.

Limitations:

 Computationally complex for large molecules.

Molecular Orbital Theory (MOT)

Key Features:

 Metal-ligand bonding is described by the formation of molecular orbitals through the

overlap of atomic orbitals from both the metal and ligands.
 Accounts for both σσ-bonding and ππ-bonding interactions.

Key Concepts:

 σσ-Bonding: Metal-ligand bonds formed by overlap of metal's dd-orbitals and

ligand's ss- or pp-orbitals.
 ππ-Bonding: Involves ππ-acceptor ligands (e.g., CO, CN⁻) where the metal donates
electron density back into the ligand’s π∗π∗-orbitals (backbonding).

Strengths:

 Explains electronic transitions, charge transfer, and magnetic properties.

 Predicts bond strength and stability accurately.

Limitations:

 Computationally intensive and requires advanced quantum mechanical calculations.

Sidgwick’s Effective Atomic Number (EAN) Rule

Key Features:

 Stability of coordination compounds is achieved when the total number of electrons

around the metal equals the nearest noble gas configuration.

Example:

 In [Fe(CN)6]4−[Fe(CN)6]4−, Fe²⁺ contributes 24 electrons, and six CN−CN− ligands

contribute 12 electrons, achieving the noble gas configuration (36 electrons for
krypton).

Limitations:

20
  Not universally applicable, especially for complexes with metals in higher oxidation
states.

Relativistic Effects on Heavy Metals

 Explains anomalies in bonding and stability for heavier elements, especially those
beyond the second transition series, such as gold (Au) and platinum (Pt).

COMPARISON OF THEORIES
Theory Advantages Limitations
Explained primary and secondary
Werner's Did not address the nature of bonding
valencies, laid the foundation of
Theory or geometries.
coordination chemistry.
Simple, explains geometry and Cannot explain colors or field strength
VBT
magnetism. variations.
Ignores covalent bonding and ligand-
Explains electronic transitions, colors,
CFT metal interactions beyond electrostatic
magnetism.
forces.
Accounts for covalency, more accurate
LFT Computationally intensive.
predictions.
MOT Provides a detailed electronic
Complex, requires advanced
description of bonding and
computations.
interactions.

4.2 VALENCE BOND THEORY (VBT)

Valence Bond Theory focuses on the overlap of metal atomic orbitals with those of ligands.
The theory explains the geometries of coordination compounds, such
as octahedral, tetrahedral, and square planar, based on the hybridization of the metal’s

21
orbitals.

Example: The coordination of ammonia to a copper ion in [Cu(NH₃)₄]² ⁺ can be explained

by the hybridization of copper’s d-orbitals to form bonds with ammonia molecules.

4.3 CRYSTAL FIELD THEORY (CFT)

CFT explains the splitting of d-orbitals in transition metal ions when ligands approach. This
theory accounts for the color, magnetic properties, and stability of metal-ligand complexes.
For example, in octahedral complexes, the five degenerate d-orbitals split into two energy
levels, and this split leads to the characteristic colors of many transition metal complexes.

Key Features of Crystal Field Theory

22
 1. Electrostatic Interaction:
o CFT assumes ligands are point charges (for ionic ligands) or point dipoles (for
neutral ligands).
o The metal-ligand interaction is purely electrostatic.

2. Splitting of d-Orbitals:
o In a free metal ion, all five dd-orbitals are degenerate (same energy).
o When ligands approach the metal ion, the dd-orbitals experience repulsion and
split into groups of different energies, depending on the geometry of the
complex.

3. Crystal Field Splitting Energy (ΔΔ):

o The energy difference between the split dd-orbitals is termed ΔΔ.
o ΔΔ depends on the ligand strength (spectrochemical series) and the geometry
of the complex.

Splitting of dd-Orbitals in Different Geometries

1. Octahedral Field

 In octahedral geometry, six ligands surround the metal ion symmetrically.

 Splitting: The dd-orbitals split into two groups:
o t2gt2g: Lower energy (dxy,dxz,dyzdxy,dxz,dyz)
o egeg: Higher energy (dz2,dx2−y2dz2,dx2−y2)

Crystal Field Splitting Diagram:

lua
Copy code
e_g (higher energy)
------
↑↑
t2g (lower energy)

 Magnitude of splitting (ΔoΔo) determines high-spin or low-spin complexes:

o Strong-field ligands (e.g., CN⁻, CO): Large ΔoΔo, favoring low-spin.
o Weak-field ligands (e.g., H₂O, Cl⁻): Small ΔoΔo, favoring high-spin.

2. Tetrahedral Field

 In tetrahedral geometry, four ligands surround the metal ion asymmetrically.

 Splitting:
o ee: Lower energy (dz2,dx2−y2dz2,dx2−y2)
o t2t2: Higher energy (dxy,dxz,dyzdxy,dxz,dyz)

Crystal Field Splitting Diagram:

lua
Copy code
t2 (higher energy)

23
 ------
↑↑
e (lower energy)

 ΔtΔt (tetrahedral splitting energy) is smaller than ΔoΔo because there are fewer
ligands, and the geometry is less symmetric.

3. Square Planar Field

 Four ligands are arranged in a square planar geometry, common for d8d8 metal ions
like Ni²⁺, Pd²⁺, and Pt²⁺.
 Splitting:
o dx2−y2dx2−y2: Highest energy
o dz2dz2: Moderate energy
o dxy,dxz,dyzdxy,dxz,dyz: Lower energy

Crystal Field Splitting Diagram:

lua
Copy code
dx2-y2 (highest energy)
------
dz2
------
dxy
dxz, dyz (lowest energy)

 Square planar complexes are typically low-spin.

Applications of CFT

1. Color of Complexes:
o Absorption of specific wavelengths of light corresponds to electronic
transitions between split dd-orbitals.
o Example: [Cu(H2O)6]2+[Cu(H2O)6]2+ appears blue due to absorption in the
red region.

2. Magnetism:
o High-spin complexes are paramagnetic (unpaired electrons).
o Low-spin complexes are diamagnetic (all electrons paired).

3. Stability of Complexes:
o Strong-field ligands stabilize complexes by increasing ΔΔ.

4. Catalysis:
o Understanding electronic structures aids in designing catalysts like
Wilkinson’s catalyst and cytochromes.

24
4.4 LIGAND FIELD THEORY (LFT)

LFT builds on CFT by using molecular orbital theory to explain bonding in coordination
compounds more accurately. It combines the idea of ligand-induced splitting of d-orbitals
with the concept of metal-ligand bonding through molecular orbitals. LFT is especially useful
for explaining the properties of complexes with a high coordination number.

Key Features of Ligand Field Theory (LFT)

1. Covalent Bonding:
o LFT introduces the concept that bonding between metal and ligands is not
purely ionic (as in CFT) but also involves covalent character.
o This covalent bonding is explained using molecular orbital theory (MOT),
which describes the interaction of metal orbitals with ligand orbitals to form
molecular orbitals.

2. Hybridization of Metal Orbitals:

o LFT suggests that the metal ion's orbitals undergo hybridization
(e.g., d2sp3d2sp3 for octahedral, sp3sp3 for tetrahedral geometries) to form
bonding and antibonding molecular orbitals.
o The strength of the ligand field influences the degree of hybridization and
bonding.

25
 3. Ligand-to-Metal and Metal-to-Ligand Bonding:
o Sigma Bonding: Ligands donate electron density into the metal’s orbitals
(e.g., donation of electron pairs from the ligand lone pairs into the metal’s
empty orbitals).
o Pi Bonding: Certain ligands (like COCO and CN−CN−) can engage in back-
donation, where the metal also donates electron density from its dd-orbitals
back into the ligand’s empty π∗π∗-orbitals, enhancing the metal-ligand bond.

4. Electron Distribution:
o The metal’s dd-orbitals and the ligand’s orbitals mix to form bonding and
antibonding molecular orbitals, leading to a more nuanced description of
bonding.
o The combination of covalent and ionic contributions explains the observed
bonding properties, magnetic behavior, and stability of complexes.

Splitting of d-Orbitals in Ligand Field Theory

Just like in CFT, LFT describes the splitting of metal dd-orbitals in different geometries, but
it considers both electrostatic and covalent effects. The interaction between the metal and
ligands results in varying degrees of orbital splitting depending on the geometry of the
complex.

1. Octahedral Field:

In an octahedral geometry, the dd-orbitals split into two sets of orbitals:

 t2gt2g orbitals (lower energy): dxy,dxz,dyzdxy,dxz,dyz

 egeg orbitals (higher energy): dz2,dx2−y2dz2,dx2−y2

The splitting is caused by the electrostatic repulsion between the metal's dd-electrons and the
ligand's electron cloud, combined with the overlap of the metal’s dd-orbitals with the ligand’s
orbitals.

2. Tetrahedral Field:

In a tetrahedral complex, the dd-orbitals split differently:

 ee orbitals (lower energy): dz2,dx2−y2dz2,dx2−y2

 t2t2 orbitals (higher energy): dxy,dxz,dyzdxy,dxz,dyz

Because of the weaker ligand-metal interactions in the tetrahedral field compared to

octahedral, the splitting energy (ΔtΔt) is smaller than in the octahedral field (ΔoΔo).

3. Square Planar Field:

In square planar complexes (typically for d8d8 metals), the dd-orbitals split in a way that
the dx2−y2dx2−y2 orbital has the highest energy, followed by dz2dz2, and then the other dd-
orbitals (e.g., dxy,dxz,dyzdxy,dxz,dyz) are at lower energy.
26
Bonding in Ligand Field Theory

1. Sigma (σσ) Bonding:

o The metal donates electron density from its dd-orbitals into the ligand’s lone
pairs. Ligands, such as water (H₂O), ammonia (NH₃), or chloride (Cl ⁻),
typically form sigma bonds through their lone pairs of electrons.
o The formation of these bonds raises the overall stability of the coordination
complex.

2. Pi (ππ) Bonding:
o Certain ligands, like carbon monoxide (CO) or cyanide (CN ⁻), are capable of
forming ππ-back bonds with the metal.
o In this interaction, the metal uses its filled dd-orbitals to donate electron
density back to the empty π∗π∗-orbitals of the ligand. This enhances the
metal-ligand bonding, especially for transition metals with low oxidation
states.

Splitting of dd-Orbitals in Different Geometries

1. Octahedral Field

 In octahedral geometry, six ligands surround the metal ion symmetrically.

 Splitting: The dd-orbitals split into two groups:
o t2gt2g: Lower energy (dxy,dxz,dyzdxy,dxz,dyz)
o egeg: Higher energy (dz2,dx2−y2dz2,dx2−y2)

Crystal Field Splitting Diagram:

lua
Copy code
e_g (higher energy)
------
↑↑
t2g (lower energy)

 Magnitude of splitting (ΔoΔo) determines high-spin or low-spin complexes:

o Strong-field ligands (e.g., CN⁻, CO): Large ΔoΔo, favoring low-spin.
o Weak-field ligands (e.g., H₂O, Cl⁻): Small ΔoΔo, favoring high-spin.

2. Tetrahedral Field

 In tetrahedral geometry, four ligands surround the metal ion asymmetrically.

 Splitting:
o ee: Lower energy (dz2,dx2−y2dz2,dx2−y2)
o t2t2: Higher energy (dxy,dxz,dyzdxy,dxz,dyz)

Crystal Field Splitting Diagram:

27
lua
Copy code
t2 (higher energy)
------
↑↑
e (lower energy)

 ΔtΔt (tetrahedral splitting energy) is smaller than ΔoΔo because there are fewer
ligands, and the geometry is less symmetric.

3. Square Planar Field

 Four ligands are arranged in a square planar geometry, common for d8d8 metal ions
like Ni²⁺, Pd²⁺, and Pt²⁺.
 Splitting:
o dx2−y2dx2−y2: Highest energy
o dz2dz2: Moderate energy
o dxy,dxz,dyzdxy,dxz,dyz: Lower energy

Crystal Field Splitting Diagram:

lua
Copy code
dx2-y2 (highest energy)
------
dz2
------
dxy
dxz, dyz (lowest energy)

 Square planar complexes are typically low-spin.

Limitations of Ligand Field Theory

1. Complex Calculations:
o LFT is computationally intensive, especially for complexes with larger metal
ions or multiple ligands, requiring advanced quantum mechanical methods.

2. Does Not Fully Describe All Bonding:

o LFT does not provide a complete picture of bonding for all complexes,
especially in systems involving multiple types of bonding (such as delocalized
bonding in organometallic complexes).

28
 CLASSIFICATION OF COORDINATION COMPOUNDS

The coordination number of a metal ion in a coordination complex refers to the number of
ligand atoms directly bonded to the metal center. The geometry of the complex is determined
by the coordination number, and this dictates the arrangement of ligands around the metal
ion. Below are the common coordination numbers and their corresponding geometries:

5.1 BASED ON COORDINATION NUMBER

Coordination compounds can be classified by the coordination number of the metal center.
Each coordination number correlates with a specific geometry:

 Coordination number 2: Linear geometry.

 Coordination number 4: Tetrahedral or square planar geometry.
 Coordination number 6: Octahedral geometry.

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Coordination Number 2: Linear Geometry

 Geometry: In complexes with a coordination number of 2, the ligands are arranged in

a straight line around the central metal ion, resulting in a linear geometry.
 Example: [Ag(NH₃)₂]⁺ (Silver-ammonia complex)
o The silver ion (Ag⁺) is surrounded by two ammonia molecules in a straight
line.

 Bonding: The ligands bond to the metal ion via sigma bonds, and the metal's electron
pairs are shared with the ligands.
 Geometry Characteristics: The bond angle between the ligands is 180°, and the
metal ion in this geometry typically has a low coordination number, which is common
in certain transition metal complexes, especially with small ligands
like Cl−Cl− or NH3NH3.

2. Coordination Number 4: Tetrahedral or Square Planar Geometry

 Geometry:
o Tetrahedral: In this geometry, four ligands are arranged symmetrically
around the metal ion in a three-dimensional structure. The bond angles
between the ligands are 109.5°.

30
 o Square Planar: In some cases, especially with transition metal ions in the +2
oxidation state, four ligands may be arranged in a flat square shape around the
metal center, with bond angles of 90°.

 Example of Tetrahedral: [NiCl₄]²⁻ (Nickel chloride complex)

o The nickel ion (Ni²⁺) is surrounded by four chloride ions in a tetrahedral
arrangement.

 Example of Square Planar: [Cu(NH₃)₄]²⁺ (Copper-ammonia complex)

o The copper ion (Cu²⁺) is surrounded by four ammonia molecules arranged in a
square planar shape.

 Bonding:
o In tetrahedral complexes, the metal-ligand interactions cause the dd-orbitals to
split, leading to the specific geometry.
o Square planar geometry typically arises from the metal’s preference for
minimizing electron-electron repulsion between the ligands, commonly seen
with d8d8 metal ions (such as Pt²⁺ and Ni²⁺).

3. Coordination Number 6: Octahedral Geometry

 Geometry: In octahedral complexes, six ligands surround the central metal ion,
forming an octahedral shape. The bond angles between the ligands are 90° and 180°.
 Example: [Fe(CN)₆]⁴⁻ (Iron-cyanide complex)
o The iron ion (Fe²⁺) is surrounded by six cyanide ions in an octahedral
arrangement.

 Bonding: The six ligands are arranged symmetrically around the metal ion,
minimizing repulsion between them. The dd-orbitals of the metal ion split into two
sets in an octahedral field (as described by Crystal Field Theory and Ligand Field
Theory), and the geometry maximizes stability for the complex.

Summary of Common Geometries Based on Coordination Number:

 Coordination Number 2: Linear geometry (180° bond angle).

 Coordination Number 4: Either tetrahedral (109.5° bond angles) or square planar
(90° bond angles) geometry.

31
  Coordination Number 6: Octahedral geometry (90° and 180° bond angles).

The geometry of a coordination compound plays a crucial role in determining its chemical
properties, reactivity, and physical characteristics, including color and magnetism. The
arrangement of ligands also influences the electronic structure and stability of the complex.

5.2 BASED ON THE TYPE OF LIGANDS

 Monodentate ligands: Ligands that coordinate via one donor atom.

 Bidentate ligands: Ligands that coordinate via two donor atoms.
 Polydentate ligands: Ligands that coordinate via multiple donor atoms.

1. Monodentate Ligands

 Definition:
Monodentate ligands are ligands that coordinate to a metal ion through only one
donor atom. These ligands can form only a single bond to the metal center.
 Characteristics:
o The donor atom has a lone pair of electrons that is donated to the metal ion to
form a bond.
o Each ligand donates one electron pair to the metal.

 Examples of Monodentate Ligands:

o Water (H₂O): The oxygen atom has lone pairs that can bond with the metal
ion.
o Ammonia (NH₃): The nitrogen atom donates a lone pair of electrons.
o Chloride (Cl⁻): The chloride ion donates a lone pair from its single negative
charge.

 Example Complex:
o [Cu(H₂O)₆]²⁺
Here, water is the monodentate ligand, coordinating via the lone pair on the
oxygen atom.

32
2. Bidentate Ligands

 Definition:
Bidentate ligands are ligands that coordinate to a metal ion via two donor atoms.
These two atoms are typically part of the same molecule or ion and donate electron
pairs to form two bonds with the metal ion.
 Characteristics:
o The ligand forms a chelate ring with the central metal atom by bonding
through two donor atoms.
o Bidentate ligands tend to form more stable complexes due to the chelation
effect, which involves the formation of a ring structure.

 Examples of Bidentate Ligands:

o Ethylene diamine (en): Contains two nitrogen atoms, each with a lone pair of
electrons that can coordinate with the metal.
o Acetylacetonate (acac): The oxygen atoms in the two carbonyl groups donate
lone pairs of electrons to the metal.
o Oxalate (C₂O₄²⁻): The two oxygen atoms from the oxalate ion each
coordinate to the metal ion.

 Example Complex:
o [Ni(en)₃]²⁺
Ethylene diamine (en) is a bidentate ligand that coordinates through the two
nitrogen atoms.

3. Polydentate Ligands

 Definition:
Polydentate ligands, also known as chelating agents, are ligands that can coordinate
to a metal ion through multiple donor atoms (more than two). These ligands can
form several bonds with the central metal atom, leading to the formation of larger
chelate rings.
 Characteristics:
o Polydentate ligands can form more than one chelate ring with the metal,
increasing the stability of the complex.
o The chelation effect becomes more pronounced as the number of donor atoms
increases, leading to highly stable coordination compounds.

 Examples of Polydentate Ligands:

o EDTA (ethylenediaminetetraacetate): This ligand has four carboxylate
groups and two amine groups, providing six donor atoms that can coordinate
to a metal ion.
o DTPA (diethylenetriaminepentaacetate): Similar to EDTA but with five
donor atoms from carboxylate and amine groups.
o Porphyrins: Organic compounds with a macrocyclic structure that contain
multiple nitrogen atoms as donor sites.

33
  Example Complex:
o [Fe(EDTA)]²⁻
EDTA is a hexadentate ligand, binding to the metal through six donor atoms
(four oxygen and two nitrogen atoms).

5.3 BASED ON THE GEOMETRY OF THE COMPLEX

The shape of the coordination complex is influenced by the coordination number and the
nature of the ligands. The most common geometries are:

 Octahedral: Common for coordination number 6.

 Tetrahedral: Common for coordination number 4 with smaller ligands.
 Square Planar: Common for coordination number 4 with larger ligands or d⁸ metal
ions.

Octahedral Geometry (Coordination Number 6)

34
  Definition:
The octahedral geometry occurs when a metal ion is coordinated by six ligands,
which are arranged symmetrically around the metal center.
 Characteristics:
o The six ligands are placed at the vertices of an octahedron, with 90° bond
angles between the ligands.
o The central metal ion has a coordination number of 6, resulting in a symmetric
and stable arrangement of ligands.

 Common Occurrence:
o This geometry is the most common for transition metal ions with a
coordination number of 6, particularly for larger or highly charged metal
ions.
o It is seen in many d⁶, d⁷, d⁸, and d¹⁰ metal complexes.

 Example Complexes:
o [Fe(CN)₆]⁴⁻ (Iron cyanide complex)
o [Co(NH₃)₆]³⁺ (Cobalt-ammonia complex)

 Bonding:
o The six ligands form sigma bonds with the metal center, and the d-orbitals of
the metal ion split due to the ligand field, which influences the electronic and
magnetic properties of the complex.

2. Tetrahedral Geometry (Coordination Number 4)

 Definition:
The tetrahedral geometry occurs when a metal ion is coordinated by four ligands,
arranged in a three-dimensional tetrahedral shape.
 Characteristics:
o The four ligands are positioned at the vertices of a tetrahedron,
with 109.5° bond angles between the ligands.
o This geometry is common for metal ions that have a coordination number of 4,
especially when the ligands are smaller and less bulky.

 Common Occurrence:
o This geometry is most common for smaller metal ions or ions with a low
charge. The metal ion's size and the ligand's size also play a role in
determining the geometry.
o Tetrahedral complexes are often observed with transition
metals like Zn²⁺ or Fe²⁺.

 Example Complexes:
o [NiCl₄]²⁻ (Nickel chloride complex)
o [ZnCl₄]²⁻ (Zinc chloride complex)

 Bonding:

35
 o In tetrahedral complexes, the ligands donate electron density into the metal's
orbitals, causing the d-orbitals to split differently compared to octahedral
geometry.

3. Square Planar Geometry (Coordination Number 4)

 Definition:
The square planar geometry is another arrangement for a coordination number of 4,
where the four ligands are placed in a flat, square-shaped arrangement around the
central metal ion.
 Characteristics:
o The four ligands are positioned at the corners of a square, with 90° bond
angles between them.
o This geometry is typically observed in complexes with d⁸ metal ions or when
the ligands are large and bulky.

 Common Occurrence:
o The square planar geometry is common for transition metal complexes with
d⁸ electron configurations(e.g., Pd²⁺, Pt²⁺, and Ni²⁺), and it is often observed
when the metal ion has a higher charge or when ligands such as ammonia
(NH₃) or cyanide (CN⁻) are involved.

Example Complex:

 [Fe(EDTA)]²⁻
EDTA is a hexadentate ligand, binding to the metal through six donor atoms (four
oxygen and two nitrogen atoms).


36
 PREPARATION AND SYNTHESIS OF COORDINATION
COMPOUNDS

The synthesis of coordination compounds involves various methods, depending on the nature
of the metal and ligands, as well as the desired properties of the final complex. Some of the
key methods for synthesizing coordination compounds include direct
synthesis, solvothermal synthesis, and precipitation methods.

6.1. METHODS OF SYNTHESIS

Coordination compounds can be synthesized through several methods:

 Direct Synthesis: Direct reaction between metal salts and ligands in a suitable
solvent.
 Solvothermal Synthesis: Carried out under controlled temperature and pressure in
solvents, often used to synthesize complexes of rare or high-valent metals.
 Precipitation Methods: Mixing solutions of metal salts and ligands to form solid
coordination complexes.

Direct Synthesis

 Definition:
Direct synthesis refers to the method where metal salts react directly with ligands in a
suitable solvent to form a coordination compound. This is one of the simplest and
most straightforward methods for preparing coordination complexes.
 Process:
o Metal salts (e.g., metal chlorides, sulfates, or nitrates) are mixed with the
appropriate ligands in a solvent (e.g., water, ethanol, or other organic
solvents).
o The metal ions interact with the donor atoms of the ligands, forming
coordinate bonds and resulting in the formation of a coordination complex.

 Example Reaction:
o [Cu(H₂O)₄]²⁺: Copper(II) sulfate reacting with water in the presence of a
suitable solvent to form a copper(II)-water complex.

 Advantages:
o Simple and cost-effective.
o Suitable for large-scale synthesis when the metal and ligand are readily
available.

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Solvothermal Synthesis

 Definition:
Solvothermal synthesis involves the synthesis of coordination compounds under
controlled temperature and pressure conditions in a solvent, often used for
synthesizing complexes of rare or high-valent metals. The solvent is usually an
organic solvent, and the reaction is carried out in a sealed vessel known as an
autoclave.
 Process:
o The metal salt and ligands are dissolved in a solvent, and the reaction is
carried out at elevated temperatures (often above the boiling point of the
solvent) and pressures.

o This method allows for the formation of complexes that are difficult to
synthesize at ambient conditions.
o Solvothermal conditions can also promote the crystallization of highly stable
or unusual coordination compounds.

 Example Reaction:
o [Ni(CO)₄]: Nickel carbonyl can be synthesized under solvothermal conditions
by reacting nickel salts with carbon monoxide at high pressure.

 Advantages:
o Ideal for synthesizing complexes involving rare metals or high oxidation
states.
o Can result in high-purity, well-defined complexes with good crystallinity.

Precipitation Methods

 Definition:
Precipitation methods involve the formation of a coordination compound by
inducing the precipitation of a solid complex from a solution. This is typically done
by adding a precipitating agent that causes the metal-ligand complex to form and
separate from the solution.
 Process:
o A metal salt is dissolved in a solvent, and a ligand (or another reactant) is
added to the solution.
38
 o The complex formed during the reaction is often insoluble in the solvent and
precipitates out, making it easy to isolate.
o Filtration or centrifugation is typically used to separate the precipitate from the
solution.

 Example Reaction:
o [Ag(NH₃)₂]Cl: Silver chloride (AgCl) can be precipitated from a solution of
silver nitrate by adding ammonia (NH₃), which reacts with silver ions to form
a silver-ammonia complex.

 Advantages:
o Simple and low-cost method for preparing coordination compounds.
o Useful for preparing large quantities of coordination complexes.

6.2. EXAMPLES OF SYNTHESIS

 [Cu(NH₃)₄]²⁺: Synthesized by reacting copper(II) sulfate with excess ammonia

solution.
 [Fe(CO)₅]: Synthesized by reacting iron metal with carbon monoxide under high
pressure.

1. [Cu(NH₃)₄]²⁺:

 Reaction: Copper(II) sulfate reacts with excess ammonia solution.

 Process: When ammonia solution is added to a copper(II) sulfate solution, the
ammonia molecules react with the copper(II) ions to form the complex
ion [Cu(NH3)4]2+[Cu(NH3)4]2+.
 Observation: The reaction often results in a deep blue solution, which is
characteristic of the tetraamminedCu(II) complex.

Equation: CuSO₄ (aq)+4NH₃ (aq)→[Cu(NH3)4]2++SO₄2−CuSO₄ (aq)+4NH₃ (aq

)→[Cu(NH3)4]2++SO₄2−

2. [Fe(CO)₅]:

 Reaction: Iron pentacarbonyl can be synthesized by reacting iron (often in the form
of iron powder) with carbon monoxide.
 Process: When iron is exposed to carbon monoxide gas under pressure and at
moderate temperatures, the metal forms a coordination complex with five carbon
monoxide ligands.
 Observation: The product, iron pentacarbonyl [Fe(CO)5][Fe(CO)5], is a volatile,
colorless liquid at room temperature.

Equation: Fe+5CO→[Fe(CO)5]Fe+5CO→[Fe(CO)5]

39
Both examples show the formation of metal complexes through the combination of metal
ions with ligands (ammonia or carbon monoxide), demonstrating common methods of
synthesizing coordination compounds in chemistry.

6.3. CHALLENGES IN SYNTHESIS

Synthesis of coordination complexes can be challenging due to the stability of intermediates,

the need for specific ligands, and the difficulties in controlling the geometry and charge of the
metal center. Tailoring the synthesis process for industrial applications requires extensive
optimization.

1. Chemical Synthesis:

 Yield and Purity: Achieving high yields and purity is often difficult. Reactions may
lead to side products, which require additional purification steps, thus lowering
overall efficiency.
 Reactivity Control: Some reactants are highly reactive, and controlling these
reactions can be tricky. Ensuring that the reaction proceeds to the desired product
without undesirable by-products is a common issue.
 Scalability: Many laboratory-scale synthesis methods don't easily translate to large-
scale production due to factors like heat management, cost, and material handling.
 Environmental Impact: Certain chemical reactions produce hazardous waste or
require toxic solvents, posing environmental risks.
 Cost of Raw Materials: Some synthesis processes require rare or expensive
chemicals, increasing production costs and limiting accessibility.
 Reaction Selectivity: Achieving the desired product without competing reactions can
be challenging, especially in complex multistep syntheses.

2. Materials Science Synthesis:

 Material Properties: Achieving desired physical, mechanical, or chemical properties

in the final product is often difficult, especially when novel materials are being
developed.
 Nanomaterials: Synthesizing nanomaterials with precise control over size, shape,
and surface properties is a significant challenge.
 Scaling Up: Many methods of creating advanced materials work well in small
quantities but are hard to scale up for industrial applications.

3. Synthesis of Ideas or Strategies:

 Integration of Diverse Inputs: Combining ideas or strategies from different fields or

perspectives can be challenging due to differences in paradigms or objectives.
 Complexity Management: As the synthesis involves multiple factors or variables,
managing and keeping track of the complex interplay of these elements can be
overwhelming.
 Uncertainty and Risk: The synthesis of ideas or strategies involves predicting
outcomes, which can be fraught with uncertainty and risk.

40
 REACTIVITY AND STABILITY OF COORDINATION COMPOUNDS

Substitution reactions are a type of chemical reaction in which one functional group or atom
in a molecule is replaced by another. These reactions are common in organic chemistry,
especially in the context of halogenated compounds and coordination chemistry. Below are
some key types of substitution reactions:

7.1. SUBSTITUTION REACTIONS

Coordination compounds undergo substitution reactions where one ligand is replaced by

another. These reactions can be ligand exchange reactions (monodentate) or chelate
exchange reactions (multidentate). These reactions are crucial in understanding the reactivity
of coordination compounds in different environments.

1. Nucleophilic Substitution:

This involves the replacement of a leaving group by a nucleophile (an electron-rich species).

 Types:
o Sₙ1 (Unimolecular Nucleophilic Substitution): The rate-determining step
involves the departure of the leaving group, forming a carbocation. The
nucleophile then attacks the carbocation.
 Example:R–Cl→R++Cl−R–Cl→R++Cl−R++Nu−→R–NuR+
+Nu−→R–Nu
o Sₙ2 (Bimolecular Nucleophilic Substitution): The nucleophile attacks the
electrophilic carbon at the same time as the leaving group departs, forming a
transition state.
 Example:R–Cl+Nu−→R–Nu+Cl−R–Cl+Nu−→R–Nu+Cl−

 Characteristics:
o Sₙ1: Occurs typically with tertiary carbocations and requires a polar solvent.

41
 o Sₙ2: Occurs with primary or secondary carbocations and requires a strong
nucleophile and a polar aprotic solvent.

 Example Reaction:
o In the reaction of 1-bromopropane with hydroxide ion (OH ⁻), a nucleophilic
substitution occurs where the bromine is replaced by a hydroxyl
group:CH₃CH₂CH₂Br+OH−→CH₃CH₂CH₂OH+Br−CH₃CH₂CH₂Br+OH−
→CH₃CH₂CH₂OH+Br−

2. Electrophilic Substitution:

This involves the substitution of a hydrogen atom in an aromatic compound by an

electrophile (electron-deficient species).

 Types:

o Aromatic Substitution: This is common in aromatic compounds, where an

electrophile replaces one of the hydrogens attached to a benzene ring.
Examples include halogenation, nitration, sulfonation, and Friedel-Crafts
reactions.
 Example (Nitration of
Benzene):C₆H₆+HNO₃→H₂SO₄C₆H₅NO₂+H₂OC₆H₆+HNO₃H₂S
O₄C₆H₅NO₂+H₂O
 Example (Friedel-Crafts
Alkylation):C₆H₆+RCl→AlCl₃C₆H₅R+HClC₆H₆+RClAlCl₃
C₆H₅R+HCl

3. Radical Substitution:

In radical substitution, a radical (an atom or molecule with an unpaired electron) replaces a
bonded atom or group.

 Example: The chlorination of methane:

CH₄+Cl₂→UV lightCH₃Cl+HClCH₄+Cl₂UV lightCH₃Cl+HCl

In this reaction, the chlorine radical replaces a hydrogen atom in methane, forming methyl
chloride (CH₃Cl).

4. Ligand Substitution (Coordination Chemistry):

In coordination chemistry, a ligand (a molecule or ion that can donate a pair of electrons)
replaces another ligand bound to a central metal atom in a coordination complex.

 Example: The substitution of chloride by ammonia in the complex [CuCl4]2−[CuCl4

]2−:[CuCl4]2−+4NH₃→[Cu(NH3)4]2++4Cl−[CuCl4]2−+4NH₃→[Cu(NH3)4]2+
+4Cl−

42
7.2. REDOX REACTIONS

Coordination compounds also participate in redox reactions, where the oxidation state of the
metal center changes. These reactions are vital in catalysis, electron transfer processes, and in
the activation of small molecules.

Key Concepts in Redox Reactions:

1. Oxidation: The process in which an atom or ion loses electrons. The oxidation state
of the element increases.
o Example: When sodium (Na) reacts with chlorine (Cl) to form sodium
chloride (NaCl), sodium undergoes oxidation.Na→Na++e−Na→Na++e−
o In this case, sodium loses one electron, becoming Na⁺.

2. Reduction: The process in which an atom or ion gains electrons. The oxidation state
of the element decreases.
o Example: When chlorine (Cl₂) gains electrons to form chloride ions (Cl⁻),
chlorine undergoes reduction.Cl2+2e−→2Cl−Cl2+2e−→2Cl−
o In this case, chlorine gains electrons and is reduced to chloride ions (Cl⁻).

3. Oxidizing Agent (Oxidant): The substance that gains electrons and gets reduced. It
causes the oxidation of another substance.
o Example: In the reaction between sodium and chlorine, chlorine (Cl₂) is the
oxidizing agent because it gains electrons.

4. Reducing Agent (Reductant): The substance that loses electrons and gets oxidized.
It causes the reduction of another substance.
o Example: In the reaction between sodium and chlorine, sodium (Na) is the
reducing agent because it loses electrons.

General Redox Reaction:

A redox reaction can be represented by:

Oxidant (gains electrons)+Reductant (loses electrons)→ProductsOxidant (gains electrons)

+Reductant (loses electrons)→Products

Example of a Redox Reaction:

Combustion of Methane:

CH₄+2O₂→CO₂+2H₂OCH₄+2O₂→CO₂+2H₂O

 In this reaction, carbon in methane (CH₄) undergoes oxidation from an oxidation

state of -4 to +4 in CO₂.
 Oxygen in O₂ undergoes reduction, going from an oxidation state of 0 to -2 in H₂O
and CO₂.

Half-Reactions:
43
Redox reactions can be broken down into two half-reactions: one for oxidation and one for
reduction.

1. Oxidation Half-Reaction: This shows the species losing electrons.

o Example: In the reaction of zinc with copper sulfate:Zn→Zn2+
+2e−Zn→Zn2++2e− Zinc is oxidized, losing two electrons.

2. Reduction Half-Reaction: This shows the species gaining electrons.

o Example: In the same reaction:Cu2++2e−→CuCu2++2e−→Cu Copper ions
(Cu²⁺) are reduced to copper metal (Cu) by gaining two electrons.

Balancing Redox Reactions:

Redox reactions must be balanced both in terms of mass and charge. This involves ensuring
that the number of electrons lost in oxidation equals the number of electrons gained in
reduction.

Types of Redox Reactions:

1. Displacement Reactions: A more reactive element displaces a less reactive element

from a compound.
o Example:Zn+CuSO₄→ZnSO₄+CuZn+CuSO₄→ZnSO₄+Cu Here, zinc
displaces copper from copper sulfate, undergoing oxidation, while copper is
reduced.

2. Combustion Reactions: Involving the burning of a substance in oxygen, typically

producing CO₂ and H₂O.
o Example: The combustion of hydrogen:2H₂+O₂→2H₂O2H₂+O₂→2H₂O

3. Respiration: A biological redox reaction where glucose (C₆H₁₂O₆) is oxidized to

produce carbon dioxide and water.
o Equation:C₆H₁₂O₆+6O₂→6CO₂+6H₂OC₆H₁₂O₆+6O₂→6CO₂+6H₂O Gl
ucose is oxidized, and oxygen is reduced to water.

4. Corrosion: The oxidation of metals, typically iron, in the presence of water and
oxygen, forming rust.
o Example:4Fe+3O₂+6H₂O→4Fe(OH)34Fe+3O₂+6H₂O→4Fe(OH)3

7.3. FACTORS AFFECTING STABILITY

The stability of coordination compounds is influenced by several factors:

1. Chelation: Multidentate ligands, which form multiple bonds with a metal ion, lead to
greater stability. This is known as the chelate effect, where chelate complexes are
more stable than those with monodentate ligands due to increased coordination and
entropic gain.

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 2. Ligand Field Strength: Strong field ligands, such as CN⁻ and NH₃, cause greater
splitting of the metal ion's d-orbitals, leading to increased stabilization. Weak field
ligands, like Cl⁻, result in smaller splitting and less stabilization.
3. Electronic Configuration of the Metal Ion: The oxidation state and d-orbital
configuration of the metal ion impact its ability to stabilize the complex. Higher
oxidation states generally form stronger complexes with ligands but may also be more
reactive.
4. Charge on Metal Ion: A higher charge on the metal ion strengthens electrostatic
attraction with ligands, enhancing stability.
5. Steric Effects: Bulky ligands can create steric hindrance, reducing the stability of the
complex.

APPLICATIONS OF COORDINATION COMPOUNDS

8.1. IN BIOLOGY

Coordination compounds are essential in biological systems. For instance:

1. Oxygen Transport and Storage:

 Hemoglobin and Myoglobin: These are proteins that contain iron-based coordination
complexes. Hemoglobin in red blood cells binds to oxygen through its iron (Fe²⁺)
center, facilitating oxygen transport in the bloodstream. Myoglobin, found in muscles,
stores oxygen by coordinating oxygen to its iron atom.
 Example: The iron in hemoglobin forms a coordination complex with oxygen,
enabling efficient transport and release of oxygen in tissues.

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2. Enzyme Function and Catalysis:

 Metalloenzymes: Many enzymes rely on metal ions (such as Fe²⁺, Cu²⁺, Mg²⁺, and
Zn²⁺) as cofactors in their active sites to catalyze biochemical reactions. These metal
ions coordinate with ligands from the enzyme's structure or substrate molecules.
 Example: Carbonic anhydrase, which uses a zinc ion to catalyze the conversion of
carbon dioxide to bicarbonate, is crucial in regulating pH and CO₂ levels in the blood.

3. Electron Transfer in Metabolism:

 Cytochromes: These are proteins containing iron or copper that play a key role in the
electron transport chain, which is essential for cellular respiration and energy
production in cells.
 Example: Cytochrome c contains a heme group (iron in a coordination complex),
which participates in electron transfer during oxidative phosphorylation.

4. DNA and RNA Interaction:

 Metal Ions in Nucleic Acid Structure: Metal ions such as Mg²⁺ help stabilize the
structure of nucleic acids (DNA/RNA) by coordinating with the phosphate backbone
and aiding in the proper folding of these molecules.
 Example: Mg²⁺ ions are critical for the function of RNA polymerase during
transcription.

5. Detoxification and Heavy Metal Poisoning:

 Chelation Therapy: Coordination compounds are used in medicine to treat poisoning

by heavy metals like lead, mercury, or arsenic. Chelating agents such

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 as EDTA or dimercaprol form stable complexes with metal ions, facilitating their
excretion from the body.

 Example: Penicillamine is used to treat Wilson's disease by binding copper ions and
promoting their removal.

8.2. IN INDUSTRIAL CHEMISTRY

Coordination compounds are used in industrial processes like catalysis, material synthesis,
and as reagents in the production of fine chemicals.

8.3. IN ENVIRONMENTAL CHEMISTRY

Coordination complexes can be used to remove pollutants from the environment. For
instance, certain metal-based complexes can capture and degrade toxic chemicals in
wastewater treatment processes.

1. Water Treatment and Purification:

 Chelating Agents in Water Softening: Coordination compounds are used to remove

metal ions, such as calcium (Ca²⁺) and magnesium (Mg²⁺), from hard water by
forming soluble chelates. This helps prevent scale formation in pipes and boilers.

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  Example: EDTA (ethylenediaminetetraacetic acid) is used to chelate metal ions
and improve the effectiveness of detergents, preventing metal ion-induced scaling in
water systems.

2. Heavy Metal Removal and Detoxification:

 Removal of Toxic Metals: Coordination compounds can be used to bind and remove
toxic heavy metals like lead (Pb²⁺), mercury (Hg²⁺), and arsenic (As³ ⁺) from
contaminated water, soil, or industrial effluents.
 Example: Dithiocarbamates and thiol-based chelating agents form stable
complexes with toxic metal ions, enabling their removal or neutralization in
wastewater treatment processes.

3. Pollution Control:

 Air Pollution and Catalysis: Certain coordination compounds act as catalysts in

processes that reduce pollutants. For example, platinum (Pt) and palladium
(Pd) complexes are used in catalytic converters in cars to convert harmful gases like
carbon monoxide (CO), nitrogen oxides (NOx), and hydrocarbons into less harmful
emissions.
 Example: Catalytic converters in automobiles use platinum and palladium
coordination compounds to convert harmful emissions into less toxic substances like
nitrogen, carbon dioxide, and water.

4. Bioremediation:

 Metals in Bioremediation: Coordination compounds are used in the process of

bioremediation to help clean up environmental contaminants. Metal-based
coordination compounds can assist microorganisms in breaking down or transforming
pollutants in contaminated environments like soil or water.
 Example: Copper-based chelates have been used to enhance the growth of bacteria
that degrade organic pollutants in soil or water.

5. Soil Remediation:

 Metal Immobilization: Coordination compounds can be applied to immobilize toxic

metals in contaminated soil, making them less bioavailable and reducing their
environmental impact. These compounds form stable complexes with the metal ions,
preventing them from leaching into groundwater or being absorbed by plants.
 Example: Phosphate-based coordination compounds can bind with toxic metals
like cadmium (Cd²⁺) in contaminated soil, reducing their mobility and preventing
plant uptake.

6. Environmental Sensing and Monitoring:

 Sensor Development: Coordination compounds are used in the development of

sensors for detecting pollutants or hazardous chemicals in the environment. Metal-
ligand complexes can be designed to change color or fluorescence in the presence of
specific ions or pollutants.

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  Example: Fluorescent chelating sensors are used to detect heavy metals like
mercury or lead in environmental samples, providing a simple and effective way to
monitor pollution levels.

8.4. IN MEDICINE

Coordination compounds play a critical role in medical treatments. Cisplatin, for example, is
a platinum-based coordination compound used in chemotherapy. Other metal-based drugs are
in development for treating various conditions

Chemotherapy:

 Platinum-based Drugs: One of the most well-known applications of coordination

compounds in medicine is in cancer treatment. Platinum-based drugs, such
as cisplatin and carboplatin, are widely used as chemotherapy agents. These drugs
form coordination complexes with DNA, interfering with DNA replication and
thereby inhibiting cancer cell growth.

 Example: Cisplatin (cis-diamminedichloroplatinum(II)) binds to the DNA of cancer

cells, causing DNA cross-linking and preventing the cells from dividing, leading to
cell death.

2. Antibacterial and Antifungal Agents:

 Silver-based Compounds: Silver ions, in coordination with ligands, are known for
their antimicrobial properties. Silver coordination compounds are used in wound care
and as topical antiseptics due to their ability to kill bacteria and prevent infection.
 Example: Silver sulfadiazine is used in treating burn wounds because of its
antibacterial and antifungal effects.

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3. Chelation Therapy:

 Treatment of Heavy Metal Poisoning: Coordination compounds are used in the

medical treatment of poisoning by heavy metals like lead, mercury, and arsenic.
Chelating agents form stable complexes with these toxic metals, allowing them to be
excreted from the body.
 Example: EDTA (ethylenediaminetetraacetic acid) and dimercaprol are
commonly used in chelation therapy to treat lead and mercury poisoning.

4. Imaging and Diagnostic Agents:

 MRI and CT Scanning: Coordination compounds are used as contrast agents in

diagnostic imaging, such as in Magnetic Resonance Imaging (MRI) and Computed
Tomography (CT) scans. Metal ions like gadolinium (Gd³⁺) are used in MRI
contrast agents to improve the visibility of internal body structures.
 Example: Gadolinium-based contrast agents (GBCA) are used in MRI to enhance
imaging of tissues and detect abnormalities, such as tumors or neurological
conditions.

5. Radiotherapy:

 Radioactive Isotopes in Therapy: Coordination compounds are used in targeted

radiotherapy, where radioactive isotopes are attached to ligands that specifically bind
to cancer cells. This enables targeted radiation therapy, delivering radioactive
treatment directly to cancerous tissues while minimizing damage to surrounding
healthy tissues.
 Example: Radionuclide therapy, such as radioactive iodine-131 for thyroid cancer,
uses coordination compounds to target cancer cells with radioactive isotopes for
treatment.

6. Oxygen Carriers:

 Artificial Blood Substitutes: Coordination compounds that mimic the oxygen-

carrying ability of hemoglobin are being developed as artificial blood substitutes.
These compounds typically involve iron or copper coordination complexes, which can
bind and release oxygen in a manner similar to hemoglobin.
 Example: Hemoglobin-based oxygen carriers (HBOCs) and perfluorocarbons
(PFCs) are being researched as alternatives for blood transfusions, especially in cases
of blood loss or emergency situations.

7. Enzyme Inhibition:

 Metal Ion Complexes as Inhibitors: Some coordination compounds act as enzyme

inhibitors, particularly in diseases involving metal-dependent enzymes. These
inhibitors can bind to the metal ion in the enzyme’s active site and prevent the
enzyme from functioning.
 Example: Ace inhibitors in the treatment of hypertension may use metal
coordination to inhibit the activity of angiotensin-converting enzyme (ACE).

8. Gene Delivery:

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  Gene Therapy: Coordination compounds are being explored for their ability to
deliver genetic material (e.g., DNA or RNA) into cells. Metal-ligand complexes can
facilitate the binding and transport of genetic material, potentially leading to targeted
therapies for genetic disorders.
 Example: Some platinum-based complexes are being researched for their potential
in gene delivery systems to treat genetic diseases.

CONCLUSION

In conclusion, this thesis underscores the pivotal role of coordination compounds in

advancing scientific understanding and practical applications across diverse domains. By
exploring the foundational concepts of coordination chemistry and examining key bonding
theories like VBT, CFT, and LFT, the thesis provides a comprehensive framework for
understanding the intricate interactions between metal centers and ligands. The synthesis
methods and reactivity studies discussed illustrate the versatility of these compounds, paving

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the way for innovations in medicine, industrial catalysis, and environmental solutions.
Through detailed case studies, the thesis highlights the transformative potential of
coordination compounds, from drug development to sustainable practices. Looking ahead,
addressing challenges such as designing novel ligands and enhancing compound stability is
crucial for expanding their utility. The thesis calls for interdisciplinary collaboration to
leverage advancements in computational chemistry, material science, and biochemistry,
ensuring the continued evolution of coordination chemistry in solving global challenges.

BIBLIOGRAPHY

 Royal Society of Chemistry (RSC)

 https://www.rsc.org
Includes articles, case studies, and resources on coordination chemistry for advanced
learners.

 American Chemical Society (ACS)

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  https://pubs.acs.org
Provides access to peer-reviewed research papers and journal articles on coordination
compounds (some resources require subscription).

 Springer Nature

 https://link.springer.com
Hosts numerous books, articles, and research papers on coordination compounds.

 Wiley Online Library

 https://onlinelibrary.wiley.com
Contains a wide range of materials on inorganic and coordination chemistry.

Books

1. "Inorganic Chemistry" by J.D. Lee

o A widely recommended textbook for understanding the fundamental concepts
of coordination chemistry.

2. "Advanced Inorganic Chemistry" by F.A. Cotton, G. Wilkinson, and P.L. Gaus

o A classic reference for detailed explanations of bonding theories, synthesis,
and applications of coordination compounds.

3. "Concise Inorganic Chemistry" by Rodger L. DeKock and Harry B. Gray

o Provides a detailed yet concise overview of the principles of inorganic and
coordination chemistry.

4. "Coordination Chemistry" by Joan Ribas Gispert

o Focuses specifically on coordination compounds, discussing their properties,
bonding theories, and applications.

5. "Chemical Applications of Group Theory" by F. Albert Cotton

o Useful for understanding the symmetry aspects of coordination compounds
and their electronic properties.

6. "Principles of Bioinorganic Chemistry" by S.J. Lippard and J.M. Berg

o Explores the role of coordination compounds in biological systems.

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