This award in the Inorganic, Bioinorganic and Organometallic Chemistry Program supports research in the laboratory of Professor Alan S. Goldman of Rutgers University to develop catalysts that will photochemically functionalize at C-H bonds. This photochemical carbonylation of hydrocarbons is based on a developing understanding of the chemical mechanisms whereby it occurs. Representative catalysts will be studied as to their kinetics, thermodynamics, and molecular orbital transformations. Systems are based on soluble late transition-metal complexes, which are promising because of their success in related catalytic processes, particularly industrial hydroformylation processes, and their unusual regioselectivity. The reverse reaction, aldehyde decarbonylation, will also be studied as it is the microscopic reverse of carbonylation and also of significant potential value. Efficiently turning the world's major carbon-containing resources, such as coal, natural gas and petroleum, into commodity chemicals and low pollution fuels is essential to a thriving economy. The chemically difficult and economically important process of adding organic functionality by activating stable C-H bonds will be undertaken using new photochemical catalysts developed in Dr. Goldman's laboratory. The development of these catalysts depends on furthering our understanding of how the catalysts work at a molecular level. The mechanism of photochemical carbonylation is to be probed in a systematic series of kinetic and thermodynamic experiments coupled with theoretical calculations.
