Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

8-9-2007

Journal or Book Title

The Journal of Organic Chemistry

Volume

72

Issue

18

First Page

6848

Last Page

6859

DOI

10.1021/jo071049r

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.

Comments

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

Rights

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Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

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