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 mol−1 (FSO2Cl).
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