CHEMISTRY OF METAL HYDRIDES .V. PREPARATION OF PLATINUM HYDRIDES FROM [PTX(CO)(R3P)2]+ AND [PTX(COOR)(PH3P)2]

The synthesis of [Pt2X2(R3P)4][BF4]2 for × = Br or I with R = phenyl, and for X = Br with R = ethyl, is described. The rates of cleavage of these dihalo-bridged diplatinum cations with carbon monoxide to give the carbonyls, trans-[PtX(CO)(R3P)2][BF4], have been studied qualitatively. trans-[PtCl(CO)(Et3P)2][BF4] reacts with water giving trans-[PtHCl(Et3P)2] and carbon dioxide. The triphenylphosphine analog, trans-[PtX(CO)(Ph3P)2][BF4], where X = Cl, Br, or I, reacts readily with methanol or ethanol giving the alkoxycarbonyl [PtX(COOR)(Ph3P)2] where R = CH3 or C2H5. These alkoxycarbonyls react with water in the presence of salt catalyst giving trans-[PtHX(Ph3P)2]. Possible mechanisms for these conversions are discussed. © 1969, American Chemical Society. All rights reserved.