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Quantum Chemical Characterization of Water Oxidation Catalysts

Miró, P.; Ertem, M. Z.; Gagliardi, L.; Cramer, C. J.
in Molecular Water Oxidation Catalysts, Llobet, A., Ed.; John Wiley & Sons: Chichester; 2014, p. 233.

We have studied and compared the water oxidation mechanism of various transition metal based water oxidation catalysts. All of the studied mononuclear catalysts (cis-[RuII(bpy)2(H2O)2]2+, [RuII(damp)(bpy)(H2O)]2+, CoHβF-CO2H and FeIII-TAML) follow a water nucleophilic attack mechanism while the studied dinuclear catalyst (in,in-[(RuII(trpy)(H2O))2(μ-bpp)]3+) follows an intramolecular O–O bond formation mechanism. Furthermore, when non-pyridine-based ligands are used, such as TAML or a hangman corrole, we have shown that the non-innocent role of the ligand plays a role in the water oxidation mechanism.