Ab initio molecular orbital calculations at the MP2/6-31G** level of theory predict that homolytic substitution by hydrogen atom and methyl radical at the sulfur atom in alkyl sulfides proceeds via T-shaped transition structures and in sulfoxides via hypervalent (9-S-3) radical intermediates.
J. E. Lyons and C. H. Schiesser, J. Chem. Soc., Perkin Trans. 2, 1992, 1655 DOI: 10.1039/P29920001655
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