This award from the Inorganic, Bioinorganic and Organometallic Chemistry Program will support research in the general area of organometallic chemistry, with particular emphasis on reactions of carbon dioxide promoted by organometallic compounds. The practical interest in such reactions derives from the strong possibility that carbon dioxide will be used as a source of carbon for chemical synthesis in the future, in for example reactions with hydrogen derived from the decomposition of water by solar energy. The long-term goal of the project is a clear mechanistic view of carbon-hydrogen, carbon-carbon and carbon-oxygen bond forming processes resulting from the insertion of carbon dioxide into M-H, M-C and M-O bonds. Reactivity studies have revealed a similarity in reaction characteristics for carbon-hydrogen and carbon-carbon bond forming reactions involving anionic octahedral metal derivatives and neutral square-planar metal complexes. It has further been shown that knowledge gained from investigating these different processes occurring on individual metal centers is transferable to metal centers where both reaction types are possible. The insight gained from transition metal-carbon dioxide chemistry will be used in exploring potential uses of carbon dioxide as a feedstock for the synthesis of organic chemicals. Specific areas to be explored include decarboxylation mechanisms of metallo-formates and -carbonates, alkyl-, aryl- and silyl-oxide chemistry of low-valent metals, studies related to C-H activation and functionalization, and catalytic processes involving carbon dioxide.
