Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

9-29-2007

Journal or Book Title

The Journal of Organic Chemistry

Volume

72

Issue

22

First Page

8235

Last Page

8242

DOI

10.1021/jo0711438

Abstract

The bond dissociation enthalpies (BDEs) of sulfur and selenium ylides have been estimated by applying MP2/6-311++G(3df,2p)//MP2/6-31G(d,p), G3, and other computational methods. Computed sulfoxide bond enthalpies were compared to experimental results to ensure the reliability of the computational methods before extending to related compounds. The examined ylides include the following:  sulfoxides, sulfilimines, S,C-sulfonium ylides, and selenoxides. Selenoxides have BDEs about 10 kcal/mol smaller than the corresponding sulfoxides. N-H sulfilimines and CH2-S,C-sulfonium ylides have low BDEs, unless the sulfilimine or S,C-sulfonium ylide is stabilized by an electronegative substituent on N or C, respectively. Incorporation of the S or Se into a thiophene or selenophene-type ring lowers the BDE for the ylide.

Comments

Reprinted (adapted) with permission from The Journal of Organic Chemistry, 72(22); 8235-8242. Doi: 10.1021/jo0711438. Copyright 2007 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