Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

11-19-2004

Journal or Book Title

Journal of the American Chemical Soiety

Volume

126

Issue

49

First Page

16058

Last Page

16065

DOI

10.1021/ja045935k

Abstract

Atomic oxygen O(3P) is a potent oxidant that has been well-studied in the gas phase. However, exploration of its reactivity in the condensed organic phase has been hampered by the lack of an appropriate source. Dibenzothiophene-S-oxide (DBTO) and related derivatives have been promoted as photochemical O(3P) sources but suffer from low quantum yields. Photolysis of dibenzoselenophene-Se-oxide (DBSeO) results in the formation of dibenzoselenophene and oxidized solvent in significantly higher quantum yields, ca. 0.1. The oxidation product ratios from toluene obtained from the photolysis of dibenzothiophene-S-oxide and the corresponding selenoxide are the same, strongly suggesting a common oxidizing intermediate, which is taken to be O(3P). An additional product, proposed to be the corresponding selenenic ester, is also observed under deoxygenated conditions. The photochemistry of diphenyl selenoxide includes a minor portion of oxidant-forming deoxygenation, in contrast to previous conclusions (Yamazaki, Y.; Tsuchiya, T.; Hasegawa, T.Bull. Chem. Soc. Jpn. 2003, 201−202).

Comments

Reprinted (adapted) with permission from Journal of the American Chemical Society; 126(49); 16058-16065. Doi: 10.1021/ja045935k. Copyright 2004 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). For any other uses, please submit a new request.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Share

COinS