Studies on polyoxo and polyperoxo-metalates: Part 7. Lanthano- and thoriopolyoxotungstates as catalytic oxidants with H2O2 and the X-ray crystal structure of Na8[ThW10O36]·28H2O

The effectiveness of salts of [LnIIIW10O36]9− (Ln=Y, La, Ce, Pr, Sm, Eu, Gd, Dy, Er, Lu) and [MIVW10O36]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 31P[1H]-NMR data for [LnIII{PW11O39}2]11− (Ln=Y, La, Ce, Pr, Nd, Sm, Eu, Tb, Ho, Er, Yb, Lu) and [CeIV{PW11O39}2]10− in the solid state, in water and in H2O2 solution are presented; these species have also been used for oxidation catalysis.