Homogeneous Photocatalytic Water Oxidation with a Dinuclear Co(III)-Pyridylmethylamine Complex.

A bis-hydroxo-bridged dinuclear Co(III)-pyridylmethylamine complex (1) was synthesized and the crystal structure was determined by X-ray crystallography. Complex 1 acts as a homogeneous catalyst for visible-light-driven water oxidation by persulfate (S2O8(2-)) as an oxidant with [Ru(II)(bpy)3](2+) (bpy = 2,2'-bipyridine) as a photosensitizer affording a high quantum yield (44%) with a large turnover number (TON = 742) for O2 formation without forming catalytically active Co-oxide (CoO(x)) nanoparticles. In the water-oxidation process, complex 1 undergoes proton-coupled electron-transfer (PCET) oxidation as a rate-determining step to form a putative dinuclear bis-μ-oxyl Co(III) complex (2), which has been suggested by DFT calculations. Catalytic water oxidation by 1 using [Ru(III)(bpy)3](3+) as an oxidant in a H2(16)O and H2(18)O mixture was examined to reveal an intramolecular O-O bond formation in the two-electron-oxidized bis-μ-oxyl intermediate, prior to the O2 evolution.