Synthesis and Study of Cationic Gold pi-Complexes

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This project is directed toward the syntheses and study of cationic, 14-electron gold(I) pi-alkene, pi-allene, and pi-alkyne complexes. Cationic gold(I) complexes have recently emerged as effective catalysts for the functionalization of C-C multiple bonds with carbon and heteroatom nucleophiles. However, the cationic, two-coordinate gold(I) pi-complexes germane to catalysis remain scarce and, as a result, little is known about the structure and reactivity of these important complexes. Execution of the proposed research activities will fill this gap in our understanding. Studies directed toward realizing this objective include analysis of 1) the ground-state structure and fluxional behavior of cationic gold(I) pi-complexes, 2) the relative binding ability pi-hydrocarbyl ligands to a cationic gold fragment, 3) the kinetics of degenerative ligand exchange of cationic gold(I) pi-complexes, and 4) the reactivity of gold pi-complexes toward nucleophiles. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Ross Widenhoefer of the Department of Chemistry at Duke University. Professor Widenhoefer's research efforts are directed, in large part, to the mechanistic analysis of the gold(I)-catalyzed addition of carbon and heteroatom nucleophiles to alkenes and allenes. Realization of the proposed activities will provide mechanistic information valuable to the ever-growing global community of researchers working toward the development of new and more efficient gold(I) catalyzed transformations for application in organic synthesis and pharmaceutical development.