The Electron-Rich Triple Bond as a Redox Reagent

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Compounds that contain the electron-rich triple bond, usually dirhenium species, will be used as redox reagents. A diphosphine bridging group will enable the redox potentials to be varied through substitution of groups within the ligand. Special emphasis will be placed on molecules having P-H and S-H bonds in order to assess the factors that influence the non-redox activity of these ligands versus their tendency to oxidatively add to the metal-metal bond. The complexes will also be used as synthetic precursors to dirhenium polyhydrides, and the novel reactivity and structural chemistry of these hydrides will be examined. The existence of stereochemical rigidity in 8-coordinate isomers of mononuclear rhenium polyhydride complexes will provide a unique opportunity to examine the importance of Re-Re versus Re-H-Re bonding in systems of a type that heretofore have only been found to exhibit fluxional behavior. %%% In this project in the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division, Dr. Richard A. Walton of Purdue University will continue studies of dirhenium complexes that contain electron rich metal-metal bonds. These compounds exhibit unusual reactivity and structures, and the results of this work will increase our basic knowledge of organometallic chemistry. Potential applications of these studies include desulfurization of certain toxic molecules and the development of better catalysts for hydrogenation processes.