Premium
H 2 O 2 activation by heteropolyacids with defect structures: the case of γ ‐[(XO 4 )W 10 O 32 ] n− (X = Si, Ge, n = 8; X = P, n = 7)
Author(s) -
Sartorel Andrea,
Carraro Mauro,
Bagno Alessandro,
Scorrano Gianfranco,
Bonchio Marcella
Publication year - 2008
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1326
Subject(s) - chemistry , crystallography , stereochemistry
DFT calculations including relativistic and solvent effects have been carried out for elucidating geometries and energies of tetra‐protonated, site‐defective, polyoxotungstates with general formula γ ‐[(XO 4 )W 10 O 32 ] n− (X = Si, Ge, n = 8; X = P, n = 7). Converging spectroscopic and computational evidence point to a unique role played by the lacunary structure, and allow to address the electronic and structural factors dictating the protonation sites and equilibria of these complexes, as well as their impact on H 2 O 2 activation. In all cases, the evolution of the four terminal WO functions, bordering the site defect on the polyoxotungstate surface, towards a bis‐aquo, bis‐oxo structure is preferred over the formation of four terminal hydroxo ligands. Substitution of these WOH 2 functions with peroxo ligands and their involvement in the oxygen transfer to an alkene acceptor is also supported by DFT calculations. Copyright © 2008 John Wiley & Sons, Ltd.