Water oxidation at a tetraruthenate core stabilized by polyoxometalate ligands: experimental and computational evidence to trace the competent intermediates

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

doi:10.1021/ja905067u

Water oxidation at a tetraruthenate core stabilized by polyoxometalate ligands: experimental and computational evidence to trace the competent intermediates

J Am Chem Soc. 2009 Nov 11;131(44):16051-3. doi: 10.1021/ja905067u.

Authors

Andrea Sartorel¹, Pere Miró, Enrico Salvadori, Sophie Romain, Mauro Carraro, Gianfranco Scorrano, Marilena Di Valentin, Antoni Llobet, Carles Bo, Marcella Bonchio

Affiliation

¹ ITM-CNR and Department of Chemical Sciences, University of Padova, via F. Marzolo 1, 35131 Padova, Italy.

PMID: 19842627
DOI: 10.1021/ja905067u

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.