Water oxidation with mononuclear ruthenium(II) polypyridine complexes involving a direct Ru(IV)═O pathway in neutral and alkaline media.

The catalytic water oxidation mechanism proposed for many single-site ruthenium complexes proceeds via the nucleophilic attack of a water molecule on the Ru(V)═O species. In contrast, Ru(II) complexes containing 4-t-butyl-2,6-di-1',8'-(naphthyrid-2'-yl)-pyridine (and its bisbenzo-derivative), an equatorial water, and two axial 4-picolines follow the thermodynamically more favorable "direct pathway" via [Ru(IV)═O](2+), which avoids the higher oxidation state [Ru(V)═O](3+) in neutral and basic media. Our experimental and theoretical results that focus on the pH-dependent onset catalytic potentials indicative of a PCET driven low-energy pathway for the formation of products with an O-O bond (such as [Ru(III)-OOH](2+) and [Ru(IV)-OO](2+)) at an applied potential below the Ru(V)═O/Ru(IV)═O couple clearly support such a mechanism. However, in the cases of [Ru(tpy)(bpy)(OH2)](2+) and [Ru(tpy)(bpm)(OH2)](2+), the formation of the Ru(V)═O species appears to be required before O-O bond formation. The complexes under discussion provide a unique functional model for water oxidation that proceeds by four consecutive PCET steps in neutral and alkaline media.