Acid-base equilibria of various oxidation states of aqua-ruthenium complexes with 1,10-phenanthroline-5,6-dione in aqueous media

Syntheses and pH dependent electrochemical properties of aqua-ruthenium(II) complexes, Ru(trpy)(PDA-N,N')(OH2)](ClO4)2 (1](ClO4)2) and Ru(trpy)(PD-N,N')(OH2)](ClO4)2 (2](ClO4)2) (trpy = 2,2':6',2'-terpyridine, PDA = 6-acetonyl-6-hydroxy-1,10-phenanthroline-5-one, PD = 1,10-phenanthroline-5,6-dione) are presented. Treatment of Ru(trpy)(PD-N,N')Cl](PF6) with AgClO4 in a mixed solvent of acetone and H2O selectively produced the acetonyl-PD complex 1](ClO4)2, and the similar treatment in a mixed solvent of 2-methoxyethanol and H2O gave the PD complex 2](ClO4)2. The molecular structures of both complexes were determined by X-ray structural analysis. The proton dissociation constants of various oxidations state of 1]2+ and 2]2+ were evaluated by simulation of E(1/2) values of those redox potentials depending on pH. The simulation revealed that the acetonyl-PD complex 1]2+ underwent successive Ru(II)/Ru(III) and Ru(III)/Ru(IV) redox couples though the two redox reactions were not separated in the cyclic voltammograms. The redox behavior of 2]2+ in H2O is reasonably explained by not only the similar successive metal-centered redox reactions but also simultaneous two-electron quinone/catechol redox couple of the PD ligand including the contribution of hydration on a carbonyl carbon.