Sulfur and Selenium Ylide Bond Enthalpies

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Date
2007-09-29
Authors
Stoffregen, Stacey
McCulla, Ryan
Jenks, William
Wilson, Robert
Cercone, Samuel
Miller, Jennifer
Jenks, William
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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.

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

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