SULFUR LIGAND COMPLEXES .9. REACTIONS OF METAL XANTHATES AND THEIR DERIVATIVES . FORMATION OF BISPHOSPHINE-DITHIOCARBONATE AND -TRITHIOCARBONATE COMPLEXES OF PALLADIUM(2) AND PLATINUM(2)

Metal xanthates react with primary and secondary amines to form dithiocarbamates. With cobalt(III) benzylxanthate, for example, the reaction with excess piperidine in tetrahydrofuran leads to ~95% conversion to the cobalt(III) dithiocarbamate complex. The formation of the monodithiocarbamate species using n-propylamine has been shown to follow second-order kinetics. Phosphines generally form adducts with dithiolates of the nickel triad elements. However, excess phosphine may produce ligand-substitution products. Quantitative formation of the bisphosphine-dithiocarbonate complexes occurs when excess methyldiphenylphosphine reacts with the benzylxanthates of palladium or platinum. These dithiocarbonates were compared with the bisphosphine-trithiocarbonate complexes of the same metal ions as prepared by direct ligand substitution on the anionic bistrithiocarbonates. Characterization reactions of the bisphosphine-dithiocarbonate species are described. © 1969, American Chemical Society. All rights reserved.