Small Molecule Activation and Materials Synthesis

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Dr. Peter Wolczanski of Cornell University proposes to investigate the chemistry of low-coordinate inorganic/organometallic complexes supported by bulky siloxide, silamide, silimide, thiolate, and acetylide ligands. In particular, the small molecule activation chemistry of these systems will be explored, and a new class of metal-organic solid state materials will be developed, with an emphasis on comprehensive training of the graduate students involved. A major goal is to generate a greater understanding of the thermodynamic aspects of C-H bond activiation by `tying` C-H bond activations to energetically similar ligand substitutions, and by measuring equilibrium isotope effects and comparing them to theory. Also, C-N bond cleavage reactions will be explored, especially as they relate to HydroDeNitrogenation processes. Mechanistic studies and systemization of oxidative addition processes of these systems is a general research goal, and studies of early transition metallaradical based C-H bond activation chemistry and metal organic solid-state compounds with covalent networks are included. The chemistry of a class of unique inorganic complexes with bonds to nitrogen, oxygen, sulfur, and carbon substituents will be studied for two reasons. One is that these compounds display unusual and unique reactivity with C-H and C-N bonds in other molecules, and have implications for improving industrial processes. The other is that they can be used as molecular precursors in the synthesis of novel materials of high complexity. These studies place experimental studies in a theoretical framework, and it is hoped that the fundamental chemistry discovered will lead to improved methods of controlling the reactivity of hydrocarbons and of designing interesting materials.