Coordination Chemistry for CSIR-NET
Module 1: Fundamentals of Coordination Chemistry
This module lays the essential groundwork. Without a strong command of these basics, you
cannot proceed to advanced topics.
1.1 Introduction to Coordination Compounds:
Werner's Theory: Primary and secondary valencies, experimental verification.
Difference between double salts and coordination compounds.
1.2 Key Terminology:
Central Metal Atom/Ion.
Ligands: Definition and types.
Classification based on Denticity: Monodentate, Bidentate (e.g., en, ox), Tridentate (e.g., dien),
Tetradentate (e.g., trien), Pentadentate, Hexadentate (e.g., EDTA).
Classification based on Charge: Anionic, Cationic, Neutral.
Special Ligands: Ambidentate (e.g., SCN⁻, NO₂⁻), Chelating Ligands, Bridging Ligands,
Flexidentate Ligands, Macrocyclic Ligands (e.g., Porphyrin, Crown ethers).
Coordination Number (CN) and Coordination Sphere.
Homoleptic and Heteroleptic complexes.
1.3 Common Geometries based on Coordination Number:
CN 2: Linear
CN 3: Trigonal Planar
CN 4: Tetrahedral and Square Planar
CN 5: Trigonal Bipyramidal and Square Pyramidal
CN 6: Octahedral (and Trigonal Prismatic)
Higher Coordination Numbers (7, 8, 9).
1.4 IUPAC Nomenclature of Coordination Compounds:
Rules for naming the cation and anion.
Order of naming ligands (alphabetical).
Prefixes for ligand numbers (di, tri, tetra vs. bis, tris, tetrakis).
Naming of anionic, cationic, and neutral ligands.
Ending of the metal name (-ate for anionic complexes).
Indicating the oxidation state of the metal (Roman numerals).
Naming of bridging ligands (μ prefix).
Module 2: Isomerism in Coordination Compounds
2.1 Structural Isomerism:
Ionization Isomerism
Hydrate (or Solvate) Isomerism
Linkage Isomerism (arising from ambidentate ligands)
Coordination Isomerism
Ligand Isomerism
Polymerization Isomerism
2.2 Stereoisomerism (Isomerism in Space):
Geometrical Isomerism (cis-trans, fac-mer):
In 4-coordinate Square Planar complexes: [MA₂B₂], [MABCD] types.
In 6-coordinate Octahedral complexes: [MA₄B₂], [MA₃B₃] (fac-mer), [M(AA)₂B₂] types.
Optical Isomerism (Chirality):
Conditions for optical activity (non-superimposable mirror image, absence of plane of
symmetry).
In 4-coordinate Tetrahedral complexes: [MABCD].
In 6-coordinate Octahedral complexes: e.g., [M(AA)₃], cis-[M(AA)₂B₂].
Determination of the total number of stereoisomers.
Module 3: Bonding in Coordination Compounds
3.1 Valence Bond Theory (VBT):
Hybridization (sp³, dsp², sp³d², d²sp³).
Correlation of hybridization with geometry.
Prediction of magnetic properties (diamagnetic/paramagnetic).
Inner Orbital (low spin) vs. Outer Orbital (high spin) complexes.
Limitations of VBT: Inability to explain color, quantitative magnetic data, and the spectrochemical
series.
3.2 Crystal Field Theory (CFT):
Postulates of CFT (ionic model).
d-orbital splitting in different fields:
Octahedral (O ) field (t₂g and eg sets).
Tetrahedral (Tₔ) field (e and t₂ sets); Relation: Δt = (4/9)Δo.
Square Planar (D₄ ) field.
Crystal Field Stabilization Energy (CFSE):
Calculation of CFSE for high-spin and low-spin complexes in octahedral fields.
Calculation of CFSE for tetrahedral complexes.
Factors affecting the magnitude of Crystal Field Splitting (Δo):
Nature of the ligands (The Spectrochemical Series).
Oxidation state of the central metal ion.
Size of d-orbitals (3d < 4d < 5d).
Geometry of the complex.
Applications of CFT: Explanation of color, magnetic properties, ionic radii variation, hydration
enthalpies, and site preference in spinels.
3.3 Jahn-Teller Distortion:
Conditions for distortion (unsymmetrical filling of t₂g or eg orbitals).
Static vs. Dynamic Jahn-Teller effect.
Consequences: Tetragonal elongation or compression in octahedral complexes (e.g., Cu(II),
high-spin Cr(II)).
3.4 Ligand Field Theory (LFT) and Molecular Orbital (MO) Theory:
Qualitative MO diagrams for octahedral complexes:
Sigma (σ) bonding only.
Sigma (σ) and Pi (π) bonding.
Explanation of the Spectrochemical Series based on π-donor and π-acceptor (π-acid) ligands.
Module 4: Electronic Spectra of Transition Metal Complexes
4.1 Basics of Electronic Spectroscopy:
Types of electronic transitions.
Term Symbols (Ground State Term Symbol calculation for dⁿ configurations using Russell-
Saunders coupling).
Hund's rules for determining the ground state term.
4.2 Selection Rules for Electronic Transitions:
Spin Selection Rule (ΔS = 0).
Laporte (Orbital) Selection Rule (Δl = ±1).
Relaxation of selection rules (spin-orbit coupling, vibronic coupling).
4.3 d-d Transitions:
Interpretation of spectra using Orgel Diagrams for d¹, d⁴, d⁶, d⁹ (D-term) and d², d³, d⁷, d⁸ (F-
term) ions in O and Tₔ fields.
Interpretation of spectra using Tanabe-Sugano Diagrams (for both high-spin and low-spin
complexes).
Calculation of Δo and Racah Parameter (B) from spectra.
4.4 Charge Transfer (CT) Spectra:
Ligand to Metal Charge Transfer (LMCT).
Metal to Ligand Charge Transfer (MLCT).
Conditions and factors affecting CT bands (very intense, fully allowed).
Module 5: Magnetic Properties of Transition Metal Complexes
5.1 Types of Magnetic Behaviour: Diamagnetism, Paramagnetism, Ferromagnetism,
Antiferromagnetism, Ferrimagnetism.
5.2 Magnetic Susceptibility and Magnetic Moment (μ).
5.3 Calculation of Magnetic Moment:
Spin-Only Formula: μ = √[n(n+2)] B.M. (where n = number of unpaired electrons).
Orbital Contribution to Magnetic Moment: Conditions for orbital contribution (unsymmetrical
filling of t₂g orbitals in O or e orbitals in Tₔ).
Temperature dependence of magnetism: Curie Law and Curie-Weiss Law.
5.4 Spin Crossover: Phenomenon where spin state changes with temperature or pressure.
Module 6: Reaction Mechanisms of Coordination Complexes
6.1 Stability of Coordination Compounds:
Thermodynamic Stability: Stepwise (K) and Overall (β) formation constants. The Chelate and
Macrocyclic effects. Irving-Williams series.
Kinetic Stability: Labile vs. Inert complexes. Explanation based on CFSE.
6.2 Substitution Reactions:
In Square-Planar Complexes:
The Trans Effect: Definition, theories (polarization and π-bonding), and synthetic applications.
Mechanism (Associative, A).
In Octahedral Complexes:
Dissociative (D), Associative (A), and Interchange (Iₐ, Iₔ) mechanisms.
Acid Hydrolysis (Aquation) and Base Hydrolysis (SN1CB mechanism).
6.3 Electron Transfer (Redox) Reactions:
Outer-Sphere Mechanism: Electron hopping without ligand bridge formation. Marcus Theory
(qualitative).
Inner-Sphere Mechanism: Reaction via a bridged intermediate. Role of bridging ligands.
Module 7: Special Topics and Applications
7.1 Bioinorganic Chemistry (Coordination Chemistry in Life):
Oxygen Transport and Storage: Hemoglobin and Myoglobin (structure, function, cooperativity,
Bohr effect). Hemerythrin and Hemocyanin.
Electron Transfer: Cytochromes, Iron-Sulfur Proteins (Ferredoxins, Rieske centers).
Enzymes: Carbonic Anhydrase, Carboxypeptidase, Superoxide Dismutase, Nitrogenase.
Photosynthesis: Role of the Mn cluster in Photosystem II.
Metals in Medicine: Cisplatin as an anti-cancer drug.
7.2 Chemistry of Lanthanides and Actinides:
Electronic configuration, oxidation states, and Lanthanide/Actinide contraction.
Coordination chemistry: Preference for high CN and O/F donor ligands.
Spectral and magnetic properties: Sharp f-f transitions, calculation of magnetic moments (L-S
coupling is significant).
7.3 Metal Clusters:
Compounds with metal-metal bonds (e.g., Re₂Cl₈²⁻, Mo₂Cl₈⁴⁻).
A brief introduction to Wade-Mingos rules for cluster electron counting.
7.4 Isopoly and Heteropoly Acids and Anions:
Structures and formulas of important polyoxometalates (e.g., of Mo, W, V).
How to Study Using This Syllabus
Follow the Order: Start with Module 1 and work your way down. The concepts are cumulative.
Connect the Dots: Constantly link new topics to old ones. For example, when studying
Electronic Spectra (Module 4), you must use your knowledge of CFT (Module 3).
Problem Solving is Key: After completing each module, solve previous years' questions (PYQs)
from CSIR-NET, GATE, and TIFR related to that topic. This is non-negotiable.
Reference Books: Use standard textbooks for in-depth understanding.
J.D. Lee: Good for fundamentals.
Huheey, Keiter, and Keiter: Excellent for concepts and bonding.
Housecroft and Sharpe (Inorganic Chemistry): Comprehensive and modern.
Ajay Kumar (Coordination Chemistry): A dedicated book on the topic, very useful for competitive
exams.