Water Oxidation at a Tetraruthenate Core Stabilized by Polyoxometalate Ligands: Experimental and Computational Evidence To Trace the Competent Intermediates
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- 作者：Andrea Sartorel ; Pere Mir ; Enrico Salvadori ; Sophie Romain ; Mauro Carraro ; Gianfranco Scorrano ; Marilena Di Valentin ; Antoni Llobet ; Carles Bo ; Marcella Bonchio
- 刊名：Journal of the American Chemical Society
- 出版年：2009
- 出版时间：November 11, 2009
- 年：2009
- 卷：131
- 期：44
- 页码：16051-16053
- 全文大小：185K
- 年卷期：v.131,no.44(November 11, 2009)
- ISSN：1520-5126
文摘
Converging UV−vis, EPR, rRaman, and DFT calculations highlight the evolution of [Ru4(H2O)4(μ-O)4(μ−OH)2(γ-SiW10O36)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.