Catalytic four-electron oxidation of water by intramolecular coupling of the oxo ligands of a bis(ruthenium-bipyridine) complex.

A bis(ruthenium-bipyridine) complex bridged by 1,8-bis(2,2':6',2''-terpyrid-4'-yl)anthracene (btpyan), [Ru(2)(μ-Cl)(bpy)(2)(btpyan)](BF(4))(3) ([1](BF(4))(3); bpy = 2,2'-bipyridine), was prepared. The cyclic voltammogram of [1](BF(4))(3) in water at pH 1.0 displayed two reversible [Ru(II),Ru(II)](3+)/[Ru(II),Ru(III)](4+) and [Ru(II),Ru(III)](4+)/[Ru(III),Ru(III)](5+) redox couples at E(1/2)(1) = +0.61 and E(1/2)(2) = +0.80 V (vs. Ag/AgCl), respectively, and an irreversible anodic peak at around E = +1.2 V followed by a strong anodic currents as a result of the oxidation of water. The controlled potential electrolysis of [1](3+) ions at E = +1.60 V in water at pH 2.6 (buffered with H(3)PO(4)/NaH(2)PO(4)) catalytically evolved dioxygen. Immediately after the electrolysis of the [1](3+) ion in H(2)(16)O at E = +1.40 V, the resultant solution displayed two resonance Raman bands at nu = 442 and 824 cm(-1). These bands shifted to nu = 426 and 780 cm(-1), respectively, when the same electrolysis was conducted in H(2)(18)O. The chemical oxidation of the [1](3+) ion by using a Ce(IV) species in H(2)(16)O and H(2)(18)O also exhibited the same resonance Raman spectra. The observed isotope frequency shifts (Δnu = 16 and 44 cm(-1)) fully fit the calculated ones based on the Ru-O and O-O stretching modes, respectively. The first successful identification of the metal-O-O-metal stretching band in the oxidation of water indicates that the oxygen-oxygen bond at the stage prior to the evolution of O(2) is formed through the intramolecular coupling of two Ru-oxo groups derived from the [1](3+) ion.