Small Molecule Activation and Coordination Chemistry

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This award by the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Peter T. Wolczanski of Cornell University to study the mechanism and thermodynamics of olefin-alkylidine rearrangements catalyzed by niobium and tantalum complexes with tris-tertbutyl silicon oxide (silox) ligands. The sulfur analog of silox will be used to explore the secondary structures of linked manganese, iron, cobalt and nickel tetrahedra to explore bio-inspired organometallic chemistry. Electronic factors involving oxygen-atom transfer are to be explored with silox-rhenium-oxo derivatives. The fundamental coordination and organometallic chemistry of square planar tungsten(IV) silox derivatives will be investigated for reactivity parallels with d8 complexes in oxidative addition reactions.Reactions of organometallic complexes with silicon-based ligands will be studied to address fundamental questions as to how these reactions proceed.