Substituent Effects on the Stability of Sulfenes

The geometries and energies of substituted sulfenes RCH═SO2 and alkenes RCH═CH2 were calculated at the HF/6-311+G(2d,p) level. An isodesmic reaction was designed to study substituent effects on the stability of sulfenes. The correlation between substituent group electronegativity χBE and the stability of sulfenes was reasonably good. Electropositive and π-acceptor substituents stabilized sulfenes while electronegative substituents destabilized them.