The crystal structures of [NMe4]2[(PhPO3){MoO(O2)2}2-{MoO(O2)2(H2O)}] and [NBun 4]2[W4O6(O2)6(OH2)(H2O)2] and their use as catalytic oxidants

The new trinuclear heteropolyperoxo complexes [NMe4]2[(RPO3){MO(O2)2}2{MO(O2)2(H2O)}](R = Ph, M = Mo 1 or W 2) have been isolated and the crystal structure of the molybdenum complex is reported. A series of analogous molybdenum complexes (R = Me, Et, Bun or But; M = Mo) have also been synthesised and characterised. The use of these compounds as catalysts for the epoxidation of alkenes, oxidation of alcohols and of tertiary amines with hydrogen peroxide as cooxidant has been studied, and complex 2 is shown to be particularly effective for such oxidations. The crystal structure of the new tetranuclear isopolyperoxo species [NBun4]2[W4O6(O2)6(OH)2(H2O)2]3 is also reported and its properties as a catalyst for alkene epoxidation with hydrogen peroxide as cooxidant studied.