Homolytic S-Cl bond dissociation enthalpies of sulfenyl chlorides – a high-level G4 thermochemical study

Numerous reactions between sulfenyl chlorides and organic molecules proceed by way of radical reactions, in which homolytic cleavage of the S-Cl bond is a key step. Owing to the lack of data concerning the quantitative effect of substituents in governing the strength of S-Cl bonds toward homolytic cleavage, the present article reports an extensive dataset of gas-phase S-Cl bond dissociation enthalpies (BDEs) obtained using the high-level G4 thermochemical protocol. The BDEs of the species in this set range from 207.2 (ONSCl) to 279.7 kJ mol⁻¹ (tBuSCl), with HSCl having a BDE of 267.6 kJ mol⁻¹. In addition, the gas-phase S-Cl BDEs of six sulfonyl chlorides have also been reported, and these range from 267.2 kJ mol^–1 (CF₃SO₂Cl) to 283.0 kJ mo1^-1 (FSO₂Cl).