A Self-improved Water Oxidation Catalyst; Is One Site Really Enough?

López, I.; Ertem, M. Z.; Maji, S.; Benet-Buchholz, J.; Keidel, A.; Kuhlmann, U.; Hildebrandt, P.; Cramer, C. J.; Batista, V. S.; Llobet, A.
Angew. Chem. Int. Ed. 2014, 53, 205 (doi:10.1002/anie.201307509).

We show for the first time that highly active mononuclear Ru-aqua water oxidation catalysts are transformed into dinuclear complexes during oxygen evolution catalysis, even from the very beginning of the catalytic process. The new dinuclear species are much more robust than their mononuclear counterparts and remain active catalysts for water oxidation, leading to the coexistence of two different catalytic cycles in solution.