The crystal structures of [NMe4][(Me2AsO2){MoO(O2)2}2], [NMe4][(Ph2PO2){MoO(O2)2}2], [NBun4][(Ph2PO2){WO(O2)2}2] and [NH4][(Ph2PO2){MoO(O2)2(H2O)}] and their use as catalytic oxidants

Abstract

The new heteropolyperoxometalate compounds [NMe₄][(Me₂AsO₂){MoO(O₂)₂}₂]1, [NMe₄][(Ph₂PO₂){MoO(O₂)₂}₂]2, [NBuⁿ₄][(Ph₂PO₂){WO(O₂)₂}₂]3 and [NH₄][(Ph₂PO₂){MoO(O₂)₂(H₂O)}]4 have been isolated and their crystal structures determined. Compounds 1–3 are dinuclear, whilst compound 4 is mononuclear; in all four structures the metal centre(s) have essentially identical pentagonal-bipyramidal co-ordination geometries with a weak axial ligand trans to an oxo group. The utility of 3 as a catalyst for the oxidation of alkenes, alcohols and tertiary amines with hydrogen peroxide as cooxidant has been studied.