With the support of the Inorganic, Bioinorganic and Organometallics Chemistry Program, Professor Gregory L. Hillhouse of the Department of Chemistry at the University of Chicago will research the chemistry of three-coordinate nickel complexes with emphasis on nickel-ligand multiple bonds including imido and carbene ligands. His group will focus their efforts first on understanding the interaction of olefins with (dtbpe)Ni=NR complexes (dtbpe = 1,2-bid(di-tert-butylphosphino)ethane) that result in NR-transfer to the olefin and the generation of aziridines. The second part or their research will focus on extending the group-transfer of imido, phosphinidene, and carbene moieties to other (heteroatom) substituted double bonds. Part three will involve the study of cationic Ni(III) imido complexes, [(dtbpe)Ni=NR+], prepared by the oxidation of the Ni(II) derivatives, to understand their bonding, magnetism, and reaction chemistries. Finally, the synthetic approaches to new multiply-bonded ligands for nickel, focusing on "carbyne" and "nitride" complexs will be examined, with the goal of isolating or trapping these highly-reactive species. This research provides a solid, fundamental understanding of the chemistry of group transfer reactions involving nickel. The studies will have impact in applied ares of inorganic chemistry and catalysis specifically relating to polymerization reactions such as olefin polymerization as well as to areas of organic synthesis related to metal-catalyzed cyclopropanations and aziridinations. This research will also provide insight into the chemistry of Ni(I) and Ni(III), rare oxidation states of emerging importance in the biological chemistry of nickel, especially in nickel-containing enzymes. In addition to the scientific contributions, this project will contribute to human resource develoment and the trianing of the next generation of scientists and teachers. Graduate, undergraduates and high school student will be integral parts of the research team. Participation of underrepresented groups, which in the past have included Hispanic, African-American, sight-disabled and women coworkers, will be actively encouraged.
