EXPERIMENTAL AND COMPUTATIONAL EVIDENCE FOR THE FORMATION OF IMINOPERSULFINIC ACIDS

An experimental and computational study of the reactions of singlet ox ygen with N-substituted sulfenamides is reported. Intermediates capabl e of epoxidizing norbornene were observed during the photooxidations o f three sulfenamides. These results are used to argue for formation of iminopersulfinic acids. The structural integrity of two iminopersulfi nic acids was supported by their successful location at the MP2/6-31G level of theory. Furthermore, the inability to locate computationally significant persulfinimide precursors suggests that the iminopersulfi nic acids form by enelike reactions involving near-simultaneous additi on of singlet oxygen to sulfur and hydrogen abstraction.