Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

1-13-2015

Journal or Book Title

The Journal of Organic Chemistry

Volume

80

Issue

3

First Page

2006

Last Page

2009

DOI

10.1021/jo502821y

Abstract

Transient carbonyl nitrenes RC(O)N, formed during thermal- or photoinduced decomposition of carbonyl azides RC(O)N3, are highly liable to the Curtius rearrangement, producing isocyanates RNCO in almost quantitative yield. Contrary to common belief, we found a thermally persistent triplet carbonyl nitrene, FC(O)N, that can be produced by flash pyrolysis of FC(O)N3 in 49% yield. The computed CBS-QB3 activation barrier for the thermal decomposition of FC(O)N3 to FC(O)N is 29 kJ mol–1 lower than that for a concerted pathway producing FNCO.

Comments

Reprinted (adapted) with permission from The Journal of Organic Chemistry; 2015: 80(3); 2006-2009. Copyright 2015 American Chemical Society.

Rights

One-time permission is granted only for the use specified in your request. No additional uses are granted (such as derivative works or other editions).

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

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