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• W2007200392 abstract "Two series of mononuclear ruthenium(II) complexes involving polypyridine-type ligands have been prepared, and their ability to act as catalysts for water oxidation has been examined. One series is of the type [Ru(tpy)(NN)Cl](PF(6)) (tpy = 2,2'; 6,2''-terpyridine), where NN is one of 12 different bidentate ligands, and the other series includes various combinations of 4-picoline, 2,2'-bipyridine (bpy), and tpy as well as the tetradentate 2,9-dipyrid-2'-yl-1,10-phenanthroline (dpp). The electronic absorption and redox data for these compounds have been measured and reported. The long-wavelength metal-to-ligand charge-transfer absorption and the first oxidation and reduction potentials are found to be consistent with the structure of the complex. Of the 23 complexes, 14 catalyze water oxidation and all of these contain a tpy or dpp. Kinetic measurements indicate a first-order reaction and together with a catalyst recovery experiment argue against the involvement of RuO(2). A tentative mechanism is proposed that involves a seven-coordinate Ru(VI)=O species that is attacked by water to form the critical O-O bond. Density functional theory calculations, which support the proposed mechanism, are performed." @default.
• W2007200392 created "2016-06-24" @default.
• W2007200392 creator A5034727905 @default.
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• W2007200392 date "2008-11-12" @default.
• W2007200392 modified "2023-09-25" @default.
• W2007200392 title "Mononuclear Ruthenium(II) Complexes That Catalyze Water Oxidation" @default.
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• W2007200392 doi "https://doi.org/10.1021/ic8014817" @default.
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