Electron transfer reactions are of fundamental biological importance but remain the least understood of the major classes of reaction mechanistic types. The most important problem is well accepted to be understanding what controls the rate of self-ET, such as that for a neutral compound reacting with its own cation radical, because it has been shown that rates for other ET reactions can be quantitatively predicted if the self- ET rates of the components are known. It has been widely believed that ET in organic compounds is principally controlled by the necessity for solvent reorganization to reach the transition state, and that internal geometry change in the substrate has only minor effects. It is suggested that interpretation of the factors controlling ET rate is currently seriously in error, and experiments to provide new experimental data to test these interpretations will be done. In contrast to most organic compounds, for which self-ET proceeds at near diffusion controlled rates, for hydrazines self-ET has is sensitive to he structure of the alkyl groups, and proceeds with rate constants >10 5 slower than diffusion control. A special series of hydrazines, sesquibicyclics, has been developed for which graduated structural changes are available, and for which detailed rate measurements as a function of temperature, solvent, and counterion will be carried out, as well as stereochemical studies. Acylated hydroxylamines and diacylhydrazines provide compounds of intermediate importance of geometry reorganization, which will allow further probing of ET rate theories, in both intra- and intermolecular reactions. These compounds are ideal for testing current theories of ET. Stereoelectronic effects on alkylation and oxidative dehydrogenation of amino nitrogen compounds will also be investigated.
