Cooperative effects in homogenous water oxidation catalysis by mononuclear ruthenium complexes†
Abstract
The homogenous water oxidation catalysis by [Ru(terpy)(bipy)Cl]+ (1) and [Ru(terpy)(Me2bipy)Cl]+ (2) (terpy = 2,2′:6′,2′′-terpyridine, bipy = 2,2′-bipyridine, Me2bipy = 4,4′-dimethyl-2,2′-bipyridine) under the influence of two redox mediators [Ru(bipy)3]2+ (3) and [Ru(phen)2(Me2bipy)]2+ (4) (phen = 1,10-phenanthroline) was investigated using Ce4+ as sacrificial oxidant. Oxygen evolution experiments revealed that mixtures of both 2–4 and 2–3 produced more molecular oxygen than catalyst 2 alone. In contrast, the combination of mediator 4 and catalyst 1 resulted in a lower catalytic performance of 1. Measurements of the temporal change in the intensity of a UV transition at 261 nm caused by the addition of four equivalents of Ce4+ to 2 revealed three distinctive regions-suggested to correspond to the stepwise processes: (i) [RuIVO]2+ → [RuVO]3+; (ii) [RuVO]3+ → [RuIII–(OOH)]2+; and (iii) [RuIII–(OOH)]2+ → [RuII–OH2]2+. UV-Visible spectrophotometric experiments on the 1–4 and 2–4 mixtures, also carried out with four equivalents of Ce4+, demonstrated a faster [Ru(phen)2(Me2bipy)]3+ → [Ru(phen)2(Me2bipy)]2+ reduction rate in 2–4 than that observed for the 1–4 combination. Cyclic voltammetry data measured for the catalysts and the mixtures revealed a coincidence in the potentials of the RuII/RuIII redox process of mediators 3 and 4 and the predicted [RuIVO]2+/[RuVO]3+ potential of catalyst 2. In contrast, the [RuIVO]2+/[RuVO]3+ process for catalyst 1 was found to occur at a higher potential than the RuII/RuIII redox process for 4. Both the spectroscopic and electrochemical experiments provide evidence that the interplay between the mediator and the catalyst is an important determinant of the catalytic activity.