Journal
JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume 607, Issue 1-2, Pages 146-155Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/S0022-328X(00)00308-9
Keywords
oxidation catalysis; X-ray crystal structure; lanthanides; thorium; polyoxotungstates
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The effectiveness of salts of [Ln(III)W(10)O(36)](9-) (Ln = Y, La, Ce, Pr, Sm, Eu, Gd, Dy, Er, Lu) and [(MW10O36)-W-IV](8-) (M = Ce, Th) as catalysts with H2O2 for alcohol oxidations and alkene epoxidations has been studied. It appears that catalysis arises from the polyperoxotungstates formed from H2O2. The X-ray crystal structure of the title complex shows that in the [ThW10O36](8-) anion the thorium has square antiprismatic geometry in which eight oxygen atoms from two W5O18 moieties form vertex-sharing bonds; Raman data suggest that the structure of the anion is retained in aqueous solution. New P-31[H-1]-NMR data for [Ln(III){PW11O39}(2)](11)- (Ln = Y, La, Ce, Pr, Nd, Sm, Eu, Tb, Ho, Er, Yb, Lu) and [Ce-IV{PW11O39}(2)](10)- in the solid state, in water and in H2O2 solution are presented; these species have also been used for oxidation catalysis. (C) 2000 Elsevier Science S.A. All rights reserved.
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