Sulfur-alkylation-initiated Cp∗Ru thiyl radicals

The sulfur-centered chemistry of Cp∗Ru(III)L (L = [S(CH2CH2S−)2] and [{HN(CH2CH2S−)2]) is dominated by redox interactions, initiated by alkylation and iodine oxidation. The Ru thiyl radicals so generated led to S-S coupling reactions, and the facile reversible homolytic dissociation of the S-S bond, substantiated by electrochemical data, contributed significantly to the rich chemistry of these systems.