Chloride oxidation catalysis by a polymeric oxide derived from [Ru(4,4′-dimethyl-2,2′-bipyridine)(Cl)3(H2O)]

Abstract

Hydrolyses of the species [Ru(4,4′-dimethyl-2,2′-bipyridine)(Cl)₃(H₂O)] and [Ru(2,2′,2″-terpyridine)(Cl)₃] yield polymeric, water-soluble oxides that function as chloride oxidation catalysts. ‘[RuDMBO₂]_x’, the polymer formed from [Ru(4,4′-dimethyl-2,2′-bipyridine)(Cl)₃(H₂O)], is described. It is characterized by UV–VIS–NIR spectroscopy, FTIR spectroscopy, electron spectroscopy for chemical analysis (ESCA) and electrochemical analyses. It exhibits significantly higher turnover numbers for electrocatalysis (>11000) and chemical catalysis (ca. 1000) than those previously reported for molecular µ-oxo dimers of ruthenium. The oxidation of chloride in aqueous solutions also yields some oxygen in the presence of [RuDMBO₂]_x. The polymer's high catalytic activity and unique structure may facilitate its incorporation into molecular photoconversion systems.