Water oxidation at a tetraruthenate core stabilized by polyoxometalate ligands: experimental and computational evidence to trace the competent intermediates.
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.
Sartorel
Andrea
A
ITM-CNR and Department of Chemical Sciences, University of Padova, via F. Marzolo 1, 35131 Padova, Italy.
Miró
Pere
P
Salvadori
Enrico
E
Romain
Sophie
S
Carraro
Mauro
M
Scorrano
Gianfranco
G
Di Valentin
Marilena
M
Llobet
Antoni
A
Bo
Carles
C
Bonchio
Marcella
M