Synthesis of Platinum(II) Hydroxycarbonyl Complexes and Related Species and Their Reactions With Hydrogen-peroxide - Existence of Organometallic Peroxy Acids

The synthesis and characterization of a class of complexes of the type P2Pt(Rx)(COOH) (P2 = (PPh3)2, (PPh2Me)2, dppe, diphoe, dppp; Rx = CF3, Me, Ph) obtained by insertion of CO into the Pt-OH bond of the corresponding hydroxo complexes is reported, together with their reactivity toward MeOH, P2Pt-(CF3)(OH), and P2Pt(CF3)(OOH) species (P2 = diphosphine). The reaction between PtCOOH and PtOH complexes leads to the formation of CO2-bridged dinuclear species. The reactions of all the carboxy compounds with hydrogen peroxide were studied with the aim of finding a synthetic route to organometallic peroxy acids. Spectroscopic studies suggest the existence of transient hydroperoxy species of the type PtCOO2H; however, attempts to exploit their oxidizing properties in the oxidation of olefins resulted only in the catalytic oxidation of carbon monoxide.