The cis-[RuII(bpy)2(H2O)2]2+ Water-Oxidation Catalyst Revisited

Authors


  • Support was received from SOLAR-H2 (EU 212508) and the MICINN (Consolider Ingenio 2010 (CSD2006-0003, CTQ2007-67918)). C.J.C. and L.G. thank the U.S. NSF (CHE-0610183) and Swiss NSF (200021-111645/1). The work at Los Alamos was supported by the LANL-LDRD program. X.S. is grateful for a Torres Quevedo contract from MICINN. bpy=2,2′-bipyridine.

Abstract

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The only operating mechanism in the oxidation of water to dioxygen catalyzed by the mononuclear cis-[RuII(bpy)2(H2O)2]2+ complex when treated with excess CeIV was unambiguously established. Theoretical calculations together with 18O-labeling experiments (see plot) revealed that it is the nucleophilic attack of water on a Ru[BOND]O group.

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