Unstable intermediates. Part CXXIII. Electron spin resonance spectra of radicals in γ-irradiated sulphuryl chloride: The SO2Cl2– radical

Abstract

The major species detected by e.s.r. spectroscopy in γ-irradiated sulphuryl chloride at 77 K is thought to be SO₂Cl₂^–. The ³³S and ³⁵Cl hyperfine components and the g-tensor components are in accord with this suggestion, and show that the radical anion is comparable with others in this class, having the unpaired electron primarily on sulphur (ca. 76%) with a very high 3s-character (ca. 29 %), and on the two equivalent chlorine atoms with a high 3p-character (ca. 23 %). The form of the molecular orbital involved is discussed.