SYNTHESIS OF POLY-YNE POLYMERS CONTAINING TRANSITION-METALS, DISILANE, DISILOXANE AND PHOSPHINE GROUPS IN THE MAIN CHAIN

The synthesis and characterization of metal poly-yne polymers containing disilane, disiloxane and phosphine groups in the main chain are described. The platinum and palladium poly-yne polymers were synthesized by polycondensation reactions between a metal chloride and an alpha, omega-bisethynyl complex in amines in the presence of cuprous iodide as a catalyst. The nickel poly-yne polymers were synthesized by an alkynyl ligand exchange reaction between a nickel acetylide and an alpha, omega-bisethynyl complex in diethylamine in the presence of cuprous iodide as a catalyst. The reaction of the platinum poly-yne polymer, containing disiloxane groups in the main chain, with copper (1) salts afforded adducts of eta-2-bonded sigma-acetylide polymer complexes. The reactions of the palladium poly-yne polymer, containing phosphine groups in the main chain, with transition-metal carbonyl complexes afforded polymer complexes which have phosphorus in the main chain-transition-metal bonds. A concentrated solution of the platinum poly-yne polymer containing disiloxane groups in the main chain forms a lyotropic liquid crystal in dichloromethane or 1,2-dichloroethane.