Photochemistry of Sulfilimine-Based Nitrene Precursors: Generation of Both Singlet and Triplet Benzoylnitrene
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The Department of Chemistry seeks to provide students with a foundation in the fundamentals and application of chemical theories and processes of the lab. Thus prepared they me pursue careers as teachers, industry supervisors, or research chemists in a variety of domains (governmental, academic, etc).
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The Department of Chemistry was founded in 1880.
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1880-present
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- College of Liberal Arts and Sciences (parent college)
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Abstract
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.
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Reprinted (adapted) with permission from The Journal of Organic Chemistry, 72(18); 6848-6859. Doi: 10.1021/jo071049r. Copyright 2007 American Chemical Society.