Water Oxidation at a Tetraruthenate Core Stabilized by Polyoxometalate Ligands: Experimental and Computational Evidence To Trace the Competent Intermediates

Andrea Sartorel; Pere Miro; Enrico Salvadori; Sophie Romain; Mauro Carraro; Gianfranco Scorrano; Marilena Di Valentin; Antoni Llobet; Carles Bo; Marcella Bonchio

doi:10.1021/ja905067u

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Water Oxidation at a Tetraruthenate Core Stabilized by Polyoxometalate Ligands: Experimental and Computational Evidence To Trace the Competent Intermediates

Journal article

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Water Oxidation at a Tetraruthenate Core Stabilized by Polyoxometalate Ligands: Experimental and Computational Evidence To Trace the Competent Intermediates

Andrea Sartorel, Pere Miro, Enrico Salvadori, Sophie Romain, Mauro Carraro, Gianfranco Scorrano, Marilena Di Valentin, Antoni Llobet, Carles Bo and Marcella Bonchio

Journal of the American Chemical Society, Vol.131(44), pp.16051-16053

11/11/2009

DOI: 10.1021/ja905067u

PMID: 19842627

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Abstract

Converging UV-vis, EPR, rRaman, and DFT calculations highlight the evolution of [Ru-4(H2O)(4)(mu-O)(4)(mu-OH)(2)(gamma-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 tetra ruthenium (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.

Chemistry

Chemistry, Multidisciplinary

Physical Sciences

Science & Technology

Details

Title: Subtitle: Water Oxidation at a Tetraruthenate Core Stabilized by Polyoxometalate Ligands: Experimental and Computational Evidence To Trace the Competent Intermediates
Creators: Andrea Sartorel - Institut Català d'Investigació Química
Pere Miro - Institut Català d'Investigació Química
Enrico Salvadori - Institut Català d'Investigació Química
Sophie Romain - Institut Català d'Investigació Química
Mauro Carraro - Institut Català d'Investigació Química
Gianfranco Scorrano - Institut Català d'Investigació Química
Marilena Di Valentin - Institut Català d'Investigació Química
Antoni Llobet - Institut Català d'Investigació Química
Carles Bo - Institut Català d'Investigació Química
Marcella Bonchio - Institut Català d'Investigació Química
Resource Type: Journal article
Publication Details: Journal of the American Chemical Society, Vol.131(44), pp.16051-16053
Publisher: Amer Chemical Soc
DOI: 10.1021/ja905067u
PMID: 19842627
ISSN: 0002-7863
eISSN: 1520-5126
Number of pages: 4
Grant note: 2009FIC00026 / Generalitat de Catalunya STPD08RCX / University of Padova (Progetto Strategico 2008, HELIOS) 2009SGR69; 2009SGR259 / Catalan Government ICIQ Foundation; Foundation CELLEX CAMERE-RBNE03JCR5 / CNR, MIUR (FIRB); Ministry of Education, Universities and Research (MIUR); Consiglio Nazionale delle Ricerche (CNR); Fund for Investment in Basic Research (FIRB) 2006034372 / PRIN; Ministry of Education, Universities and Research (MIUR); Research Projects of National Relevance (PRIN) University and Research Commission of Innovation University and Enterprise Department of Catalan Government and European Social CTQ2007-67918/BQU; CTQ2008-06549-C02-02/BQU / MICINN of the Spanish Government; Ministry of Science and Innovation, Spain (MICINN); Spanish Government CSD2006-0003 / Consolider Ingenio 2010; Ministry of Science and Innovation, Spain (MICINN); Spanish Government
Language: English
Date published: 11/11/2009
Academic Unit: Chemistry
Record Identifier: 9984618646302771

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