This grant from the Organic Dynamics Program supports the work of Professor Silas C. Blackstock at Vanderbilt University. Electron transfer mediated fragmentations and rearrangements will be examined. In particular, fragmentations of nitrogen-containing substrates such as diazenes, nitroso compounds, and azooxides, and rearrangements of methylenecyclopropane and allyl vinyl ether will be examined under oxidative conditions. Short lived radical ion intermediates will be spectroscopically characterized by low temperature solid state and solution ESR methods. The structures of the radical ion intermediates will be engineered to enhance their lifetimes in order to allow their direct observations. Reaction rate measurements to determine electron transfer mediated rate accelerations and product analysis to evaluate mechanistic hypotheses will also be conducted. %%% The removal of an electron from an organic molecule frequently results in cleavage of the molecule or rearrangement of the connectivity of its atoms. In this project a variety of carbon and nitrogen containing substrates will be used to examine these reactions. These processes are energetically costly or nonexistant in the neutral precursors. This work will study the electron deficient intermediates directly in order to understand how electron transfer accelerates these reactions. Knowledge gained from this study will facilitate informed development of new electron transfer applications in organic chemistry.
