The conditions for the formation of aryldisulphide ions, RS,during the direct reaction of sulphur with thiolate ions RShave been studied by the use of spectroelectrochemistry in dimethylacetamide. The series of derivatives examined was R = p-tolyl ( I ) , phenyl (2), 8-quinolyl (3), 2and 4-pyridyl (4), (5), N-oxido 4-pyridyl (6), 2and 4-nitrophenyl ( 7 ) , ( 8) , and 2-(5-nitropyridyl) (9). Sulphur reaction leads to RS,ions and precedes the oxidation to diaryldisulphide RS,R and polysulphide ions S:-. With derivatives (I )-(3), both reactions are successive and practically stoicheiometric, while for derivatives containing electron-withdrawing groups (6)-( 9), the equilibrium constants have been measured.Analysis of the reaction products by methylation of several solutions of thiolate ions [ (2), ( 7 ) , (8)] in the presence of sulphur confirmed the possibility of obtaining aryldisulphide ions stabilized in aprotic dipolar media.

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ChemInform Abstract The aryldisulfide ions are generated by electroreduction of (I) in the presence of sulfur. The rate constants of their reaction with the halides (II) to yield (IV) are up to ten times higher than those of the corresponding formation of (III).