Dr. Gregory L. Hillhouse, Chemistry Department, University of Chicago, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division to develop metal mediated reactions of nitrous oxide and related species. Synthetic methods will be developed for oxygen, sulfur, and imido group transfer reactions using nitrous oxide, orgnoazides, and related species. These studies will focus on the late transition metals chosen so that reductive elimination reactions will result in the clean formation of cyclic organic molecules that contain oxygen or nitrogen heteroatoms. Systems will be constructed in which the metal catalyzes these transformations. Novel insertion reactions of sulfur atoms into late transition metal-carbon bonds will be devised.
One of today's greatest chemical challenges is the selective oxidation of organic substrates. A very attractive oxidant is nitrous oxide, a molecule which liberates only nontoxic and environmentally friendly nitrogen gas after it serves as an oxygen transfer agent. Moreover, nitrous oxide is recognized as both a `greenhouse gas` and a stratospheric `ozone depleter`; it would be advantageous to find new uses for this gas, which is now an underutilized biproduct of the chemical industry. In this project metal systems will be designed to activate nitrous oxide toward oxygen atom transfer reactions and metal catalysts will be developed to facilitate these reactions. As a result new uses for nitrous oxide and some related species will be developed.
