Conversions of Ruthenium(III) Alkyl Complexes to Ruthenium(II) through Ru−Calkyl Bond Homolysis

Single-electron oxidation of the Ru(II) complexes TpRu(L)(L‘)(R) (L = CO, L‘ = NCMe, and R = CH 3 or CH 2 CH 2 Ph; L = L‘ = PMe 3 and R = CH 3 ) with AgOTf leads to alkyl elimination reactions that produce TpRu(L)(L‘)(OTf) and organic products that likely result from Ru−C alkyl bond homolysis. Density functional calculations on TpRu(CO)(NCMe)(Me) and its Ru(III) cation indicate that the Ru−CH 3 homolytic bond dissociation enthalpy is substantially reduced (48.6 to 23.2 kcal/mol) upon oxidation.