This grant in the Organic Dynamics Program supports the research of Professor Stephen F. Nelsen at the University of Wisconsin/Madison. Radical cations and dications generated by oxidation of tetrasubstituted C=C, C=N, N=N, oxygenated N=N, and trisubstituted N=S functionalities will be studied. By successive removal of one and two electrons from the double bonds, species with one unit of positive charge (radical cations) and two units of positive charge (dications) will be generated. The stability of these reactive intermediates as a function of geometry will be pursued by incorporating them into bicyclic rings. Variation of the ring size will permit an investigation of reactivity as a function of ring size and through-space interactions across medium sized rings. A variety of spectroscopic and electrochemical techniques will be used to characterize radical cations and dications. ESR will be the prime spectroscopic tool that will be used to elucidate structural details. The generation, stabilization, and characterization of reactive intermediates formed under oxidative conditions will advance the fundamental understanding of organic oxidation reactions and define the important role of molecular structure in facilitating or inhibiting oxidations.
