Polymerization of ortho-Substituted Phenylacetylenes with Well-Defined Ruthenium-Alkylidene Catalysts and Related Metathesis Initiators

The polymerization of (2-isopropoxyphenyl)acetylene was investigated using a wide range of well-defined ruthenium-alkylidene complexes and related olefin metathesis initiators. In view of its superior activity, the second generation Hoveyda-Grubbs catalyst was singled out for further studies. Only phenylacetylenes ortho-substituted with alkoxy, ester, fluoro, and silyl groups afforded polymers with moderate molecular weights. They were characterized by various analytical techniques, and their properties were pared with those of samples prepared using Rh and W initiators. The Ru-based polymers possessed high trans contents and took a helical conformation with predominantly one-handed screw sense when chiral side-chains were present.