Polymerization of substituted acetylenes by (mesitylene)M(CO)3 (M=W,Mo)

Summary Phenylacetylene could be polymerized by (mesitylene)W(CO)₃ in CCl₄ to give a polymer with 12,000 in ca. 80% yield. UV irradiation was unnecessary unlike the W(CO)₆–CCl₄-h catalyst. The present polymerization did not proceed in toluene. The (mesitylene)W(CO)₃ catalyst afforded high molecular weight polymers from phenylacetylenes bearing bulky substituents (e.g., Me₃Si and CF₃) at the ortho position. The Mo counterpart, (mesitylene)Mo(CO)₃, catalyzed the polymerization of 1-chloro-2-phenylacetylene and 1-chloro-1-octyne to provide high molecular weight polymers . Catalytic amounts of Lewis acids accelerated the polymerization of phenylacetylene by (mesitylene)W(CO)₃, but decreased the polymer molecular weight; this polymerization proceeded not only in CCl₄ but also in toluene.