Contrasting effects of redox potentials on the rate constants of oxidation and hydrolysis reactions in ruthenium complexes

We report in this work the rate constant of oxidation by peroxydisulfate of the ammine ruthenium center in [(bpy)2Ru(μ-5-CNphen)Ru(NH3)5]4+ (bpy = 2,2′-bipyridine and 5-CNphen = 5-cyano-1,10-phenanthroline) and the rate constant of hydrolysis of coordinated acetonitrile in [Ru(TPTZ)(bpy)(CH3CN)]2+ (TPTZ = 2,4,6-tris(2-pyridil)-1,3,5-triazine). With these data and literature values of related reactions, we establish the existence of contrasting effects of redox potentials of Ru3+/2+ couples on the rates of both processes.