New Powerful and Oxidatively Rugged Dinuclear Ru Water Oxidation Catalyst: Control of Mechanistic Pathways by Tailored Ligand Design

A new powerful and oxidatively rugged pyrazolate-based water oxidation catalyst of formula {[RuII(py-SO3)2(H2O)]2(μ-Mebbp)}–, 1(H2O)2–, has been prepared and thoroughly characterized spectroscopically and electrochemically. This new catalyst has been conceived based on a specific ligand tailoring design, so that its performance has been systematically improved. It was also demonstrated how subtle ligand modifications cause a change in the O–O bond formation mechanism, thus revealing the close activation energy barriers associated with each pathway.