Unit 1:
Concepts and Metal Carbonyls[12 h]History and overview of organometallic compounds. Classification and nomenclature, classes of ligands, hapticity. 18-electron and 16-electron organometallic compounds. Metal carbonyls synthesis and bonding, donor and acceptor properties of CO, binding modes of CO, polynuclear carbonyls, metal-metal bonding in M-CO clusters. Cluster valence electron (CVE) count – Wade-Mingos rule, capping rule, Mingos rule – CVE based structure prediction. IR spectral features of metal carbonyls. Reactions and activation of metal carbonyls. Metal nitrosyl (M-NO) compounds – bonding and structural features comparison with metal carbonyl.
Unit 2:
Structure and Bonding in Organometallic Compounds[12 h]Fragment molecular orbitals (FMO) of various organic and inorganic moieties like CH3, CH2, CH, BH2, BH, NH2 and NH. Walshs diagram of hetero di and triatomic molecule. Inorganic fragments MLn with varying number of L. Symmetry and shape of their FMOs. Isolobal concept, isoelectronic and isolobal relationships between various organic and inorganic fragments. Structure and bonding between various organic and inorganic fragments based on MO level diagrams.
Unit 3:
Metal with Phosphine, Alkyl, Aryl and ?-donor Ligands [10 h]Metal phosphines compounds-bonding and structural features. Organometallic compounds with ?-donor ligands like olefins, acetylenes and allyl moieties. Structure and bonding of metal derivatives of cyclic ?-donors – metallocenes, sandwich/half-sandwich compounds, bent metallocenes, metal carbenes Fischer carbenes and Schrock carbenes. Metal alkyl and aryl derivatives.
Unit 4:
Stereochemistry and Reactions of Organometallic Compounds[12 h]Stereochemically non-rigid molecules, fluxional nature of organometallic compounds, characterization of non-rigidity by spectroscopic methods. Reactions involving various organometallic compounds – oxidative addition, reductive elimination, migratory insertion -1,1 and 1,2-type insertion, elimination reactions, cyclometalation and ortho-metalation reactions and agostic interactions. Ligand substitution processes, nucleophilic and electrophilic additions regioselectivity, and abstraction reactions. Coupling reactions, Pauson-Khand reaction and olefin oxidation.
Unit 5:
Industrial Applications of Organometallic Compounds[14 h]Homogeneous and heterogeneous organometallic catalysis – principle, mechanism and their applications. Alkene hydrogenation using Wilkinsons catalyst, water-gas shift reaction, Monsanto process and Cativa Process. Hydro-formylation reactions, Wacker process, Ziegler-Natta polymerization of alkenes, Fischer-Tropsch process, olefin-metathesis – Grubbs, HoveydaGrubbs and Schrock catalysts. Palladium based catalysts – Heck, Stille, Negishi, Suzuki-Miyaura, Sonogashira, Kumada, Hiyama and Buchwald-Hartwig couplings. Organometallic compounds as drugs, sensors, radiopharmaceuticals and tracers.