Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

5-29-2008

Journal or Book Title

The Journal of Organic Chemistry

Volume

73

Issue

12

First Page

4398

Last Page

4414

DOI

10.1021/jo702654q

Abstract

Time-resolved infrared (TRIR) spectroscopy, product studies, and computational methods were applied to the photolysis of sulfilimines derived from dibenzothiophene that were expected to release acetylnitrene, trifluoroacetylnitrene, mesylnitrene, and tosylnitrene. All three methods provided results for acetylnitrene consistent with literature precedent and analogous experiments with the benzoylnitrene precursor, i.e., that the ground-state multiplicity is singlet. In contrast, product studies clearly indicate triplet reactivity for trifluoroacetylnitrene, though TRIR experiments were more ambiguous. Product studies suggest that these sulfilimines are superior sources for sulfonylnitrenes, which have triplet grounds states, to the corresponding azides, and computational studies shed light on the electronic structure of the nitrenes.

Comments

Reprinted (adapted) with permission from The Journal of Organic Chemistry, 73(12); 4398-4414. Doi: 10.1021/jo702654q. Copyright 2008 American Chemical Society.

Rights

One-time permission is granted only fo rthe use specified in your request. No additional sues are granted (such as derivative works or other editions). For any other uses, please submit a new request.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

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