Dr. Gregory L. Hillhouse, Chemistry Department, University of Chicago, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division for research into the chemistry of three-coordinate nickel complexes containing nickel-ligand multiple bonds. There are three parts of the project. The first will concentrate on studies of the bonding and reactivity of imido, phosphinidene, and carbene complexes of Ni. This work will be aimed at defining the fundamental nature of Ni-ligand multiple bonds. The second part involves Ni(I) and emphasizes the preparation of derivatives with a range of ancillary ligands for reactivity studies and spectroscopic characterization, which will prove useful in detecting and characterizing Ni(I) intermediates. Elucidation of the organometallic chemistry of Ni(I)-alkyl complexes will also be a focus. These studies also will help to better define the Ni(I)/Ni(II) redox couple and assess its implications for reactivity. The third part involves studies of the unusual, 3-coordinate Ni(II) complex cations, which are proving to possess exceptional reactivity.
This research will provide a solid understanding of the chemistry of nickel(I), a rare oxidation state, but one of emerging importance in the biological chemistry of nickel, especially in nickel-containing enzymes. Additionally, these studies will have impact in applied inorganic chemistry and catalysis, specifically in areas relating to polymerization reactions effected by nickel(II) cations, such as olefin polymerization and CO/olefin copolymerizations, and organic synthesis, such as metal-catalyzed cyclopropanations and aziridinations. In addition to the scientific contributions, this project will contribute to human resource development and the training of the next generation of scientists and teachers. Both undergraduates and high school students will be integral parts of the research team. Participation of underrepresented minorities, which in the past have included Hispanic, African- American, and women coworkers, will be actively encouraged.
