An electron spin resonance study of some sulphonyl radicals in solution

Abstract

The solution e.s.r. spectra of a series of alkane-, arene- and alkoxy-sulphonyl radicals are reported. The magnitudes of the proton hyperfine splittings in the alkanesulphonyl radicals –[graphic omitted]H–[graphic omitted]H–[graphic omitted]H–SO₂ follow the unusual order |a|(β-H) > |a|(α-H)≃|a|(γ-H). For the alkane- and arene-sulphonyl radicals evidence is found for the presence of hindered rotation about the C–S bond. t-Butoxyl radicals react with sulphur dioxide to form t-butoxysulphonyl radicals with a rate constants of ca. 10⁷–10⁸ l mol^–1 s^–1 at –40°.