Catalytic water oxidation by an in situ generated ruthenium nitrosyl complex bearing a bipyridine-bis(alkoxide) ligand.

Oxidative degradation and transformation of catalysts are commonly observed in water oxidation by molecular catalysts, especially when a highly oxidizing reagent such as (NH4)2[Ce(NO3)6] [Ce(IV)] is used. We report herein the synthesis of a ruthenium(III) complex bearing an oxidative resistant bipyridine-bis(alkoxide) ligand, [Ru(bdalk)(pic)2]+ (1, H2bdalk = 2,2′-([2,2′-bipyridine]-6,6′-diyl)bis(propan-2-ol), pic = 4-picoline) as a water oxidation catalyst (WOC). A ruthenium(II) nitrosyl complex [Ru(Hbdalk)(NO)(pic)2]2+ (3) was also formed during the water oxidation process by 1/Ce(IV), and was isolated and structurally characterized. Complex 3 was found to be an active WOC, with the nitrosyl group remaining intact during water oxidation.