Structural, Physicochemical, and Reactivity Properties of an All-inorganic, Highly Active Tetraruthenium Homogeneous Catalyst for Water Oxidation

Several key properties of the water oxidation catalyst Rb8K2[{(Ru4O4)-O-IV(OH)(2)(H2O)(4)}(gamma-SiW10O36)(2)] and its mechanism of water oxidation are given. The one-electron oxidized analogue [{(RuRu3O6)-Ru-V-O-IV(OH2)(4)}(gamma-SiW10O36)(2)](11-) has been prepared and thoroughly characterized. The voltammetric rest potentials, X-ray structures, elemental analysis, magnetism, and requirement of an oxidant (O-2) indicate these two complexes contain [(Ru4O6)-O-IV] and [(RuRu3O6)-Ru-V-O-IV] cores, respectively. Voltammetry and potentiometric titrations establish the potentials of several couples of the catalyst in aqueous solution, and a speciation diagram (versus electrochemical potential) is calculated. The potentials depend on the nature and concentration of counterions. The catalyst exhibits four reversible couples spanning only ca. 0.5 V in the H2O/O-2 potential region, keys to efficient water oxidation at low overpotential and consistent with DFT calculations showing very small energy differences between all adjacent frontier orbitals. The voltammetric potentials of the catalyst are evenly spaced (a Coulomb staircase), more consistent with bulk-like properties than molecular ones. Catalysis of water oxidation by [Ru(bpy)(3)](3+) has been examined in detail. There is a hyperbolic dependence of O-2 yield on catalyst concentration in accord with competing water and ligand (bpy) oxidations. O-2 yields, turnover numbers, and extensive kinetics data reveal several features and lead to a mechanism involving rapid oxidation of the catalyst in four one-electron steps followed by rate-limiting H2O oxidation/O-2 evolution. Six spectroscopic, scattering, and chemical experiments indicate that the catalyst is stable in solution and under catalytic turnover conditions. However, it decomposes slowly in acidic aqueous solutions (pH < 1.5).