Sulfur-alkylation-initiated Cp*Ru thiyl radicals

Abstract The formation of thiyl radicals from [Cp ∗ Ru III {κ 3 SSS ′-tpdt}] ( 1A ) and [Cp ∗ Ru III {κ 3 SSN -apdt}] ( 1B ) {Cp ∗  = η 5 -C 5 Me 5 ; tpdt = S(CH 2 CH 2 S − ) 2 ; apdt = HN(CH 2 CH 2 S − ) 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.