Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

2-1996

Journal or Book Title

Journal of Organic Chemistry

Volume

61

Issue

4

First Page

1275

Last Page

1283

DOI

10.1021/jo951504w

Abstract

An ab initio computational study on a series of sulfoxides is reported. The SO bond dissociation energy (BDE) of sulfoxides in which the sulfur atom is included in a formally aromatic ring (e.g., thiophene sulfoxide) is found to be decreased by as much as 25 kcal/mol, compared to DMSO. A complementary effect is observed for sulfoxides in which the sulfur is included in a formally antiaromatic ring (e.g., thiirene sulfoxide), in which SO BDEs are increased by as much as 15 kcal/mol. Both effects are attenuated by benzannulation. Examination of calculated geometries and isodesmic reactions with pure hydrocarbons leads to the conclusion that the observed effects are due to a severe disruption of the (anti) aromaticity of the sulfur-containing ring on oxidation. The cyclic sulfoxides appear to be neither significantly aromatic nor antiaromatic by energetic considerations. No significant SO bond strength effect is observed for simple conjugation. Inversion barriers for several sulfoxides are also calculated.

Comments

Reprinted (adapted) with permission from Journal of Organic Chemistry 61 (1996): 1275, doi:10.1021/jo951504w. Copyright 1996 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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