UNIT – I MAIN GROUP CHEMISTRY:
Chemistry of boron – borane, higher boranes, carboranes, borazines and boron nitrides. Chemistry of silicon – classification of silicates- silanes- silicon nitrides- silicones. P-N compounds, linear and cyclophosphazenes – S-N compounds – S2N2, S4N4, (SN)x, polythiazyl compounds – S-N cations and anions, S-P compounds – molecular sulphides such as P4S3, P4S7, P4S9 and P4S10.Ionic model –lattice energy – Born-Lande equation – Kapustinskii equation – high Tc superconductors.
UNIT – II PRINCIPLES OF COORDINATION CHEMISTRY:
Studies of coordination compounds in solution – detection of complex formation in solution – stability constants – stepwise and overall formation constants. Simple methods (potentiometric, pH metric and photometric methods) of determining the formation
constants. Factors affecting stability – statistical and chelate effects – forced configurations.
UNIT – III THEORIES OF METAL-LIGAND BOND:
Crystal field theory – splitting of d-orbitals under various geometries – factors affecting splitting – CFSE and evidences for CFSE (structural and thermodynamic effects). Spectrochemical series – Jahn-Teller distortion – spectral and magnetic properties of complexes – site preferences. Limitations of CFT – ligand field theory – MO theory – sigma- and pi-bonding in complexes – Nephelauxetic effect – the angular overlap model.
UNIT – IV REACTION MECHANISM IN COORDINATION COMPLEXES:
Kinetics and mechanism of reactions in solution – labile and inert complexes – ligand displacement reactions in octahedral and square planar complexes – acid hydrolysis, base hydrolysis and anationreactions. Trans effect – theory and applications – electron
transfer reactions – electron exchange reactions – complementary and noncomplementary types – inner sphere and outer sphere processes – application of electron transfer reactions in inorganic complexes – isomerisation and racemisation reactions of complexes. Molecular rearrangements of four- and six-coordinate complexes – interconversion of stereoisomers – reactions of coordinated ligands – template effect and its applications for the synthesis of macrocyclic ligands – unique properties.
UNIT – V INORGANIC PHOTOCHEMISTRY:
Electronic transitions in metal complexes, metal-centered and charge-transfer transitions – various photophysical and photochemical processes of coordination compounds. Unimolecular charge-transfer photochemistry of cobalt(III) complexes – mechanism of CTTM, photoreduction – ligand-field photochemistry of chromium(III) complexes – Adamson’s rules, photoactive excited states, V-C model – photophysics and photochemistry of ruthenium – polypyridine complexes, emission and redox properties. Photochemistry of organometallic compounds – metal carbonyl compounds – compounds with metal-metal bonding – Reinecke’ssalt chemical actinometer.