Water Oxidation at a Tetraruthenate Core Stabilized by Polyoxometalate Ligands: Experimental and Computational Evidence To Trace the Competent Intermediates
Journal of the American Chemical Society2009Vol. 131(44), pp. 16051–16053
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Andrea Sartorel, Pere Miró, Enrico Salvadori, Sophie Romain, Mauro Carraro, Gianfranco Scorrano, Marilena Di Valentin, Antoni Llobet, Carles Bó, Marcella Bonchio
Abstract
Converging UV-vis, EPR, rRaman, and DFT calculations highlight the evolution of [Ru(4)(H(2)O)(4)(mu-O)(4)(mu-OH)(2)(gamma-SiW(10)O(36))(2)](10-), 1, to high-valent intermediates. In analogy with the natural enzyme, five different oxidation states, generated from 1, have been found to power the catalytic cycle for water oxidation. A high electrophilic tetraruthenium(V)-hydroxo species is envisaged as the competent intermediate, undergoing nucleophilic attack by an external water molecule as a key step in the formation of a new O-O bond under catalytic conditions.
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