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Article
Effects of Conjugation and Aromaticity on the Sulfoxide Bond
Journal of Organic Chemistry
  • William S. Jenks, Iowa State University
  • Nikita Matsunaga, Iowa State University
  • Mark S. Gordon, Iowa State University
Document Type
Article
Disciplines
Publication Version
Published Version
Publication Date
2-1-1996
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
Citation Information
William S. Jenks, Nikita Matsunaga and Mark S. Gordon. "Effects of Conjugation and Aromaticity on the Sulfoxide Bond" Journal of Organic Chemistry Vol. 61 Iss. 4 (1996) p. 1275 - 1283
Available at: http://works.bepress.com/william_jenks/25/