Abstract
Radicals which mediate in the oxidation of thiols with the TiIII–H2O2 couple and CeIV and of disulphides with the former reagent, in aqueous solution at room temperature, have been studied by e.s.r. spectroscopy. The e.s.r. evidence establishes that signals with g ca. 2·01 and 2·005 are those of sulphinyl (RSO˙) and sulphonyl (RSO2˙) radicals, respectively. Radicals of both these types are detected in almost all instances; thiyl radicals (RS˙) cannot be detected directly but their involvement is demonstrated by spin-trapping methods; and two dithiols yield spectra with g ca. 2·013 which are attributed to cyclic disulphide radical-anions. Reaction mechanisms consistent with the e.s.r. data and earlier product studies are suggested.
Published Version
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