Contrasting Effects of Redox Potentials on the Rate Constants of Oxidation and Hydrolysis Reactions in Ruthenium Complexes

VERGARA M.M; GARCÍA POSSEM.E; LIS DE KATZ N. D; FAGALDE, FLORENCIA; KATZ, NÉSTOR E

JOURNAL OF COORDINATION CHEMISTRY

TAYLOR & FRANCIS LTD

Lugar: Londres; Año: 2011 vol. 2443 p. 2443 - 2449

0095-8972

We report in this work the rate constant of oxidation by peroxydisulfate of the ammine ruthenium center in [(bpy)2Ru(-5-CNphen)Ru(NH3)5]4þ (bpy¼2,20-bipyridine and 5- CNphen¼5-cyano-1,10-phenanthroline) and the rate constant of hydrolysis of coordinated acetonitrile in [Ru(TPTZ)(bpy)(CH3CN)]2þ (TPTZ ¼ 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 Ru3þ/2þ couples on the rates of both processes2Ru(-5-CNphen)Ru(NH3)5]4þ (bpy¼2,20-bipyridine and 5- CNphen¼5-cyano-1,10-phenanthroline) and the rate constant of hydrolysis of coordinated acetonitrile in [Ru(TPTZ)(bpy)(CH3CN)]2þ (TPTZ ¼ 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 Ru3þ/2þ couples on the rates of both processes