
%0 Journal Article
%A Ginsburg, Jack Leon 
%A Darvesh, Katherine Valenta 
%A Axworthy, Patricia 
%A Langler, Richard Francis 
%T An <emph type="2">Ab Initio</emph> Molecular Orbital Study of Sulfur-Substituted Carbanions: Toward an Understanding of Regiochemistry in the Chlorination of Unsymmetrical Sulfides
%J Australian Journal of Chemistry
%D 1997/08/19
%V 50
%N 6
%P 517-522
%K 
%R https://doi.org/10.1071/C96187
%U https://www.publish.csiro.au/paper/C96187 
%X Moller-Plesset molecular orbital calculations at the 6-31+G(d) level have been completed on substituted dimethyl sulfide-derived carbanions. The results are applied to the prediction of regiochemistry for chlorination of unsymmetrical sulfides. Notwithstanding the need for future improvements, regiochemical predictions based on stabilities of sulfur-substituted carbanions match experimental results better than earlier predictions based on stabilities of sulfur-substituted carbonium ions or sulfur-substituted free radicals. The present results suggest that the mechanism for the elimination step in the Pummerer rearrangement of a chlorosulfonium cation is an E 1cb-like process. 
