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5288471 
Journal Article 
Photochemistry of sulfilimine-based nitrene precursors: generation of both singlet and triplet benzoylnitrene 
Desikan, V; Liu, Y; Toscano, JP; Jenks, WS 
2007 
Yes 
Journal of Organic Chemistry
ISSN: 0022-3263
EISSN: 1520-6904 
72 
18 
6848-6859 
English 
17685655 
WOS:000248978900027 
Photolysis of N-benzoyl-S,S-diphenylsulfilimine or N-benzoyl dibenzothiophene sulfilimine produces PhNCO and also benzoylnitrene. Direct observation of the triplet nitrene, energetic differences between the singlet and triplet state of the nitrene, and oxygen quenching experiments suggest that the triplet nitrene derives from the triplet excited state of the sulfilimine precursors, rather than through equilibration of nearby singlet and triplet states of the nitrene itself. In acetonitrile, the formation of an ylide, followed by cyclization to the corresponding oxadiazole, is the predominant nitrene chemistry, occurring on the time scale of a few microseconds and few tens of microseconds, respectively. Trapping experiments with substrates such as cis-4-octene suggest that reactivity of the nitrene is mainly through the singlet channel, despite a fairly small energy gap between the singlet ground state and the triplet.