Sunlight-Driven Dehydrogenative Oxidation Photocatalysis by a Mononuclear Complex Acting as both Chromophore and Catalyst

Under simulated solar irradiation in the visible spectral region, the catalytically active RuIV-oxo species [Ru(O)(bpy)(tppz)]2+ (tppz = tetrapyridylpyrazine, a strongly π-accepting tridentate N, N, N-ligand) is produced directly from a single metal-to-ligand charge-transfer (MLCT) photoexcitation of the resting RuII-aquo complex [Ru(H2O)(bpy)(tppz)]2+ in aqueous media containing an electron acceptor. This photoinduced path to 2-electron/2-proton activation of a mononuclear catalyst (i.e., without a paired chromophoric unit) is enabled by the thermodynamic instability of the intermediate RuII...