E.s.r. spectroscopy has been employed to demonstrate that the reaction of +˙NH3(from TiIII and +NH3OH) with thiols (RSH) proceeds via the initial formation of thiyl radicals (RS·); these react further to give disulphides as well as oxygen-containing radicals RSO· and RSO2·, formed by a series of one-electron oxidation reactions, and both SO2–˙ and SO3–˙(which arise via sulphur dioxide formed in the decomposition of RSO2˙). Reaction with disulphides, which leads to the detection of sulphinyl radicals and disulphide-conjugated radicals, is thought to involve both radical-cations (RSSR+˙) and ammoniumyl adducts [RS([graphic omitted]H3)SR] whose further reactions have been described.
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Gilbert et al. (1980) studied this question.
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