SOME SYNTHESES OF PLATINUM-GERMANIUM COMPLEXES

A new series of compounds containing platinum-germanium bonds has been prepared from solutions of trichlorogermane in concentrated hydrochloric acid. The tetramethylammonium salt of hydridopentakis(trichlorogermyl)platinate(II), [(CH3)4N]2HPt(GeCl3)5, and the yellow isomer of the tetramethylammonium salt of dichlorobis(trichlorogermyl)platinate-(II), [(CH3)4N]2Cl2Pt(GeCl3)2, can be precipitated from such solutions under different conditions. The red isomer of tetramethylammonium dichlorobis(trichlorogermyl)platinate(II) is precipitated from a nitrobenzene solution of the tetramethylammonium hydridopentakis(trichlorogermyl)platinate(II) by the addition of diethyl ether. Various phosphonium salts and phosphine complexes also can be prepared from the hydrochloric acid solutions. Triphenylphosphonium tetrachlorobis-(trichlorogermyl)platinate(IV), [(CeH5)3PH]2Cl4Pt(GeCl3)2, and a yellow complex, chloro(trichlorogermyl)bis(triphenylphosphine)platinum(II), [(C6H5)3P]2ClPt(GeCl3), are formed under different conditions. Triphenylphosphonium tetrachlorobis(trichlorogermyl)platinate(IV) loses hydrogen chloride reversibly to form a different yellow complex, dichlorobis-(trichlorogermyl)bis(triphenylphosphine)platinum(IV), [(C6H5)3P]2Cl2PtCGeCl3)2. A white solid, trichloro(trichlorogermyl)-bis(triphenylphosphine)platinum(IV), [(C5H6)3P]2Cl3Pt(GeCl3), is precipitated from a solution of cis-dichlorobis (triphenylphosphine)platinum(II) in acetone-diethyl ether by the addition of trichlorogermane. Direct treatment of (Cl3PPtCl2)2 with trichlorosilane gives (Cl3PPtSiCl3)x; treatment with trichlorogermane gives (Cl3PPtGeCl3)x. There is some evidence for the formation of a Ni-Ge complex in the reaction of trichlorogermane with nickel(II) chloride in nitromethane solution. © 1968, American Chemical Society. All rights reserved.