Sulfur-alkylation-initiated Cp∗Ru thiyl radicals

The formation of thiyl radicals from [Cp∗RuIII{κ3SSS′-tpdt}] (1A) and [Cp∗RuIII{κ3SSN-apdt}] (1B) {Cp∗ = η5-C5Me5; tpdt = S(CH2CH2S−)2; apdt = HN(CH2CH2S−)2} has been initiated by thiolate alkylation or oxidation with iodine. Subsequent electron transfer processes yielded disulfide-bridged dinuclear complexes. The mechanistic pathways of these processes will be discussed.