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Photochemistry of Sulfilimine-Based Nitrene Precursors:  Generation of Both Singlet and Triplet Benzoylnitrene
The Journal of Organic Chemistry
  • Vasumathi Desikan, Iowa State University
  • Yonglin Liu, Johns Hopkins University
  • John P. Toscano, Johns Hopkins University
  • William S. Jenks, Iowa State University
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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.

Reprinted (adapted) with permission from The Journal of Organic Chemistry, 72(18); 6848-6859. Doi: 10.1021/jo071049r. Copyright 2007 American Chemical Society.

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Vasumathi Desikan, Yonglin Liu, John P. Toscano and William S. Jenks. "Photochemistry of Sulfilimine-Based Nitrene Precursors:  Generation of Both Singlet and Triplet Benzoylnitrene" The Journal of Organic Chemistry Vol. 72 Iss. 18 (2007) p. 6848 - 6859
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