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 α, ω‐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 α, ω‐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 (I) salts afforded adducts of η‐2‐bonded σ‐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.