Mediator-assisted water oxidation by the ruthenium “blue dimer” cis , cis -[(bpy) 2 (H 2 O)RuORu(OH 2 )(bpy) 2 ] 4+

Light-driven water oxidation occurs in oxygenic photosynthesis in photosystem II and provides redox equivalents directed to photosystem I, in which carbon dioxide is reduced. Water oxidation is also essential in artificial photosynthesis and solar fuel-forming reactions, such as water splitting into hydrogen and oxygen (2 H2 O + 4 hν → O2 + 2 H2 ) or water reduction of CO2 to methanol (2 H2 O + CO2 + 6 hν → CH3 OH + 3/2 O2 ), or hydrocarbons, which could provide clean, renewable energy. The “blue ruthenium dimer,”cis ,cis -[(bpy)2 (H2 O)RuIII ORuIII (OH2 )(bpy)2 ]4+ , was the first well characterized molecule to catalyze water oxidation. On the basis of recent insight into the mechanism, we have devised a strategy for enhancing catalytic rates by using kinetically facile electron-transfer mediators. Rate enhancements by factors of up to ≈30 have been obtained, and preliminary electrochemical experiments have demonstrated that mediator-assisted electrocatalytic water oxidation is also attainable.