Ruthenium‐incorporated, metathesis‐active polyacetylene

Two olefin metathesis methods have been developed for the preparation of metal-incorporated polyacetylene (MIPA) with high levels of covalently attached ruthenium complex. Treatment of freshly prepared, porous polyacetylene (PA) formed by polymerization of acetylene by the metathesis catalyst (H2IMes)RuCl2(CHPh)(3-bromopyridine)2 (G2B) with additional G2B resulted in the incorporation of the ruthenium complex into the solid polymer in levels up to 75% by mass, giving two-step MIPA (MIPA2). Alternatively, single-step MIPA (MIPA1) samples with similar levels (up to 79% by mass) of ruthenium incorporation were obtained by polymerization of acetylene with highly concentrated solutions of G2B, and the resulting materials formed fine suspensions in CH2Cl2. A variety of experiments confirmed that both the methods give materials with ruthenium covalently attached to PA chains. Shiny, tough MIPA films were obtained by pressing the black powders obtained by either method. Some MIPA properties were dependent on the amount of metal incorporation, but even samples with high incorporation levels mimicked untreated PA in many respects. MIPA1, but not MIPA2, was made electrically conductive by doping with iodine. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1061–1072, 2009