Proton dissociation of an aqua-Ru-quinone complex, [Ru(trpy)(q)(OH2)]²⁺ (trpy = 2,2′ : 6′,2″-terpyridine, q = 3,5-di-t-butylquinone) proceeded in two steps (pKa = 5.5 and ca. 10.5). The first step simply produced [Ru(trpy)(q)(OH)]⁺, while the second one gave an unusual oxyl radical complex, [Ru(trpy)(sq)(O−.)]⁰ (sq = 3,5-di-t-butylsemiquinone), owing to an intramolecular electron transfer from
... [Show full abstract] the resultant O²⁻ to q. A dinuclear Ru complex bridged by an anthracene framework, [Ru2(btpyan)(q)2(OH)2]²⁺ (btpyan = 1,8-bis(2,2′-terpyridyl)anthracene), was prepared to place two Ru(trpy)(q)(OH) groups at a close distance. Deprotonation of the two hydroxy protons of [Ru2(btpyan)(q)2(OH)2]²⁺ generated two oxyl radical Ru-O−. groups, which worked as a precursor for O2 evolution in the oxidation of water. The [Ru2(btpyan)(q)2(OH)2](SbF6)2 modified ITO electrode effectively catalyzed four-electron oxidation of water to evolve O2 (TON = 33500) under electrolysis at +1.70 V in H2O (pH 4.0). Various physical measurements and DFT calculations indicated that a radical coupling between two Ru(sq)(O−.) groups forms a (cat)Ru-O-O-Ru(sq) (cat = 3,5-di-t-butylcathechol) framework with a μ-superoxo bond. Successive removal of four electrons from the cat, sq, and superoxo groups of [Ru2(btpyan)(cat)(sq)(μ-O2⁻)]⁰ assisted with an attack of two water (or OH⁻) to Ru centers, which causes smooth O2 evolution with regeneration of [Ru2(btpyan)(q)2(OH)2]²⁺. Deprotonation of an Ru-quinone-ammonia complex also gave the corresponding Ru-semiquinone-aminyl radical. The oxidized form of the latter showed a high catalytic activity towards the oxidation of methanol in the presence of base.