The reactions of the ammoniumyl radical-cation (NH3+·) with sulphides and sulphoxides: an electron spin resonance investigation

Abstract
The results are described of an e.s.r. study of the reactions of NH3 +˙, generated from the TiIII–NH2OH couple, with a variety of sulphides and sulphoxides. Signals detected from sulphides include those from dimer radical-cations (R2SSR2 +˙), as well as those derived by hydrogen loss (e.g.˙CHMeSEt from Et2S) and fragmentation [e.g.˙CH2SCH2CO2H from (HO2CCH2)2S]. Sulphoxides give rise to alkyl and alkanesulphonyl (RSO2˙) radicals, the latter of which are evidently derived from sulphinic acids formed in situ. Reactions of NH3 +˙ with both types of substrate are interpreted in terms of the initial formation of radical adducts [RṠ– NH3 +, R2Ṡ(O)NH3 +] which can then undergo a variety of reactions, including substitution and fragmentation.

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