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Issue 8, 2012
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Experimental and quantum chemical characterization of the water oxidation cycle catalysed by [RuII(damp)(bpy)(H2O)]2+

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Abstract

The water-oxidation catalytic activity of [RuII(damp)(bpy)(H2O)]2+ has been determined from manometric and mass spectroscopy studies. Mechanistic details of the catalytic cycle have been studied both experimentally and using DFT and CASSCF/CASPT2 calculations. Characterisation of this Ru(II) complex and more highly oxidized catalytic intermediates has been accomplished through UV-vis and XAS spectroscopy, as well as through electrochemical techniques. Comparison of XAS spectra with CASSCF/CASPT2 calculations provides insight into the electronic structures of the more highly oxidized species, especially the degree to which oxidation occurs over both atoms of the Ru–O fragment. 18O-labelling experiments indicate that the O–O bond formation step proceeds via a water nucleophilic attack mechanism, and a detailed DFT analysis of the catalytic cycle predicts that step to be rate-determining and to take place for a formal Ru(V)[double bond, length as m-dash]O species. A number of alternative higher energy pathways have also been characterised in order to provide a more complete vision of the whole system.

Graphical abstract: Experimental and quantum chemical characterization of the water oxidation cycle catalysed by [RuII(damp)(bpy)(H2O)]2+

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Publication details

The article was received on 31 Mar 2012, accepted on 14 May 2012 and first published on 15 May 2012


Article type: Edge Article
DOI: 10.1039/C2SC20399E
Citation: Chem. Sci., 2012,3, 2576-2586
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    Experimental and quantum chemical characterization of the water oxidation cycle catalysed by [RuII(damp)(bpy)(H2O)]2+

    L. Vigara, M. Z. Ertem, N. Planas, F. Bozoglian, N. Leidel, H. Dau, M. Haumann, L. Gagliardi, C. J. Cramer and A. Llobet, Chem. Sci., 2012, 3, 2576
    DOI: 10.1039/C2SC20399E

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