1. Development of Catalytic Reactions using Well-Defined Monomeric Cu(I)
Complexes with Non-Dative Heteroatomic Ligands: Fundamental Exploration
of Scope and Mechanism of C-X (X = N, O or S) Bond Forming Reactions
T. Brent Gunnoe, North Carolina State University, Department of Chemistry
Homogeneous catalysis using well-defined and tunable transition metal complexes has impacted nearly every realm of the chemical industry including commodity scale processes and fine chemical synthesis. Many commercially applied catalysts are based on second and third row metals, and many of these are from the group of expensive "precious" metals. Developing efficient catalytic transformations with first row transition metals offers potential advantages; however, our understanding of catalytic activity of these metals lags behind second and third row congeners. We have been studying Cu-catalyzed carbon-heteroatom bond forming reactions using isolable, monomeric and well-defined Cu(I) amido, alkoxo, sulfido and related complexes. We have demonstrated that these complexes can catalyze the addition of N-H, O-H and S-H bonds across carbon-carbon multiple bonds (both inter- and intramolecular reactions), have pursued mechanistic studies of aryl amination reactions, and have begun to establish trends in 15N NMR of amido ligands as a function of metal-amido bonding.