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

Abstract

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 Ru^3+/2+ couples on the rates of both processes.

Keywords:

• Linear free energy relationships
• Redox reactions
• Nitrile hydrolysis

Acknowledgments

To CONICET, ANPCyT, and UNT (Argentina) for financial support. F. Fagalde and N.E. Katz are members of the Research Career (CONICET, Argentina).