| Abstract
| - Photolysis of N-benzoyl-S,S-diphenylsulfilimine or N-benzoyl dibenzothiophene sulfilimine producesPhNCO and also benzoylnitrene. Direct observation of the triplet nitrene, energetic differences betweenthe singlet and triplet state of the nitrene, and oxygen quenching experiments suggest that the tripletnitrene derives from the triplet excited state of the sulfilimine precursors, rather than through equilibrationof nearby singlet and triplet states of the nitrene itself. In acetonitrile, the formation of an ylide, followedby cyclization to the corresponding oxadiazole, is the predominant nitrene chemistry, occurring on thetime scale of a few microseconds and few tens of microseconds, respectively. Trapping experimentswith substrates such as cis-4-octene suggest that reactivity of the nitrene is mainly through the singletchannel, despite a fairly small energy gap between the singlet ground state and the triplet.
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