Polymers containing functional groups with versatile reactivity in the main chain are expected to serve as useful reactive precursors for main chain functional polymers. In the course of our studies to create polymers having reactive organometallic units in the main chain, we describe herein the synthesis and reactions of organometallic polymers containing cobaltacyclopentadiene and titanacyclopentadiene units in the main chain. Polymers having metallacyclopentadiene units were prepared by the reaction of diynes with low-valent organometallic complexes. Especially, polymers produced from aromatic terminal diynes such as 2,5-dialkoxy-1,4-diethynylbenzenes and a low-valent titanium complex generated in situ from titanium(IV) isopropoxide have the regioregular main chain linkage whose polymer reactions proved to be suitable for production of p-conjugated organic polymers. For example, polymers containing conjugated diene, thiophene, phenylene, and phosphole systems in the main chain were produced by the reactions of the polymers with hydrochloric acid, sulfur monochloride, propargyl bromide, and dichloroalkylphosphines, respectively. Polymers obtained through these reactions exhibited p-conjugated characters judging from their UV-vis absorption and photoluminescence spectra.
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