In this project in the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division, Lappin will continue his studies of chiral induction in electron transfer reactions between metal ion complexes. This is a relatively new field that has become an international endeavor and is attracting increasing attention from the chemical community. While it is a very basic research area, potential applications of the results in the design and manufacture of pharmaceuticals are possible. The principal goal of the project will be the provision of further details on the origins and interpretation of stereoselectivity. The relationship between chiral induction in outer-sphere reactions and chiral recognition in ion pairs formed as intermediates along the reaction coordinate will be explored. Besides kinetic studies and product analysis, the work will use NMR methods to investigate weak interactions between ions in solution to obtain structural information. A second aspect involves ligands of biological importance - amino acids and oligopeptides - and will focus on the additive effects of chiral substituents on ligand structure. Experiments with cyclodextrins will be initiated. The final portion of the work will exploit recent success in the detection of stereoselectivity in inner-sphere reactions.
