Course

Unit 1:

Theories and Concepts on d-block Coordination Compounds. [15 h]Werners coordination theory, valence bond theory (VBT), crystal field theory (CFT) CFSE – effects of CFSE, types of ligands. Spectrochemical series, spectral and magnetic properties, and nephelauxetic effect. Crystal field splitting – Oh, Td, square planar, square pyramidal and trigonal pyramid geometries, factors affecting the magnitude of CFSE, isomerism in coordination complexes, Jahn-Teller (JT) distortion – manifestation on spectral properties. Limitations of CFT. Molecular orbital theory and ligand field theory.

Unit 2:

Spectral and Magnetic Properties[15 h]Russell-Saunders coupling schemes, term symbols for various dn ions, Orgel diagrams for dn systems, ligand field parameters, Dq, Racah parameter B and nephelauxetic constant. Tanabe-Sugano diagrams – applications. Charge-transfer transitions MLCT and LMCT. Selection rules – spin-orbit and vibronic coupling effects. Spectral behaviour of f-block coordination complexes. Magnetic properties of coordination complexes – magnetic susceptibility – the contribution of spin-orbit coupling on eff, types of magnetic behaviour – para, ferro, anti-ferro and ferri-magnetic systems. Curie and Curie-Weiss laws. Guoy, Faraday and SQUID methods. Kotani plots – effects of temperature on magnetic behaviour, multinuclear homo- and heterometallic 3d, 4d and 5d systems and mixed 3d-4f systems.

Unit 3:

Reaction Mechanism[13 h]Complex equilibrium – formation constants, factors affecting stability, stability constants. Mechanisms of ligand displacement and addition reactions, cis- and trans-effect and substitution reactions. Kinetic and thermodynamic consequences on reaction pathways. Mechanism – dissociation, interchange, association and conjugate base. Stereochemical aspects. Isomerisation of chelate rings, sigma and pi bonding effects. Oxidation-reduction reactions, inner and outer sphere electron transfer reactions.

Unit 4:

Complexes of Inner Transition Elements [8 h]Oxidation states, shapes of f-orbitals (4f and 5f), nature of bonding of f-orbitals with ligands, ligand preferences, coordination numbers and the geometry of the complexes. Influence of lanthanide and actinide contraction in their coordination behaviour. Various types of coordination compounds of lanthanides and actinides.

Unit 5:

Application of Coordination Compounds[9 h]Medicinal applications – sodium nitroprusside complex for hypertension treatment. Cancer therapy platinum and palladium anticancer agents, nonplatinum anticancer agents mechanism of action. Vanadium compounds – mechanism of action. Electrochemical application – mechanism of an electrochemical process involving labile complexes, electrochemical process in a real system copper cyanide and gold cyanide system, electro reduction of tin(II) and zinc(II) complexes. Electrochemical deposition of alloys.

CO01: Apply the various theories of coordinate bonding to predict the geometry and properties of complexes as well as their stereochemistry.

CO02: Interpretation of electronic spectra of transition and inner transition metal complexes through various theories.

CO03: Improve their analytical and critical thinking skills by studying the various reaction mechanisms.

CO04: Acquire the knowledge to identify the magnetic properties of transition and inner transition metal complexes, and the latest electrochemistry and medical applications advancements.

Recommended Readings

1.Cotton, F.A., Wilkinson, G., Murillo, C.A. and Bochmann, M., 1999. Advanced inorganic chemistry. John Wiley and Sons, Inc.

2.Huheey, J.E., Keiter, E.A., Keiter, R.L. and Medhi, O.K., 2006. Inorganic chemistry: principles of structure and reactivity. Pearson Education India.

3.Lee, J.D., 2008. Concise inorganic chemistry. John Wiley & Sons.

4.Douglas, B.E., McDaniel D. and Alexander J. 2000. Concepts and models of inorganic chemistry. Wiley.

5.Atkins, P. and Overton, T., 2010. Shriver and Atkins’ inorganic chemistry. Oxford University Press, USA.

6.J. E. House, Inorganic Chemistry, Academic Press, 2008.

7.Gopalan, R., 2001. Concise coordination chemistry. Vikas publishing house.

8.Jones, C.J. and Thornback, J.R., 2007. Medicinal applications of coordination chemistry. Royal Society of Chemistry.

9.Day, M.C. and Selbin, J., 1969. Theoretical inorganic chemistry.