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Mechanism of Water Oxidation for the Ru-Hbpp Catalyst

Recent research from the research groups of Professors Laura Gagliardi and Christopher J. Cramer.

The binuclear catalyst in,in-{[RuII(trpy)(H2O)]2(μ-bpp)}3+ (Ru-Hbpp; trpy is 2,2':6',2"-terpyridine, bpp is 2,6-bis(pyridyl)-pyrazolate) facilitates the generation of molecular oxygen from water. This water oxidation step is the key bottleneck currently associated with the development of commercial light harvesting devices for the photo-production of H2 from water. Through a combination of density functional theory and multireference wave function theory computations carried out by Mehmed Z. Ertem and Tanya K. Todorova, the Gagliardi and Cramer groups were able to rationalize mechanistic and kinetic details consistent with experimental data developed in the group of collaborator Antoni Llobet of the Institute of Chemical Research of Catalonia, establishing an intramolecular pathway for O–O bond formation. This work is described in a full paper recently published in the Journal of the American Chemical Society, 2009, 131, 15176 (DOI: 10.1021/ja9036127) and should prove particularly useful for the design of improved water-splitting catalysts for future applications.

Theory indicates the active catalytic pathway to be the clockwise (intramolecular) alternative above.

Rate-determining transition-state structure e for oxygen generation from water by the binuclear Ru-Hbpp catalyst (ligand H atoms omittted for clarity).

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