This grant from the Organic Dynamics Program supports the work of Professor Stuart W. Staley at Carnegie Mellon University. Dynamic processes in bicyclooctatetraenyl dianions will be examined by nuclear magnetic resonance spectroscopy. The activation barriers for bond shifting and charge transfer will be determined by complete line shape analysis, saturation transfer, or by other NMR methods. The difference between these values will be equated to "pure" charge transfer in the absence of any major conformational change. These charge transfer rates are related to electronic coupling under conditions of solvent-separated ion pairing and cation transfer under conditions of contact ion pairing. The rates will be measured as functions of the identities of the bridging group, cation, and solvent. %%% Electron transfer from ring to ring in compounds containing two rings separated by spacer groups will be examined. These studies will be conducted under conditions in which a positively charged species (a cation) is and is not tightly associated with the electron-rich ring. The rate at which the electrons transfer as a function of spacer group connecting the two rings will provide valuable information on the ability of the spacer to act as a conduit for electron transfer. The effect of solvent on the electron transfer will also be examined.
