Synthesis,characterization, and metal complexes of polyacetylenes with pendant 2,2′‐bipyridyl groups |
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| Authors: | Jos Vicente Juan Gil‐Rubio Natalia Barquero |
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| Institution: | José Vicente,Juan Gil‐Rubio,Natalia Barquero |
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| Abstract: | 5‐Ethynyl‐2,2′‐bipyridine ( 1 ; bpyC≡CH) polymerized in the presence of catalytic amounts of RhF(COD)(PPh3)] or Rh(μ‐OH)(COD)]2 (COD = 1,5‐cyclooctadiene) in 74–91% yields. In contrast, Rh(μ‐X)(NBD)]2 (X = Cl or OMe; NBD = norbornadiene) did not catalyze the polymerization of 1 or gave low yields of the polymer. The obtained polymer, poly(5‐ethynyl‐2,2′‐bipyridine) 2 ; (bpyC?CH)n], was highly stereoregular with a predominant cis–transoidal geometry. Random copolyacetylenes containing the 2,2′‐bipyridyl group with improved solubility in organic solvents were obtained by the treatment of a mixture of 1 and phenylacetylene ( 3 ) or 1‐ethynyl‐4‐n‐pentyl‐benzene with catalytic amounts of RhF(COD)(PPh3)]. A block copolymer of 1 and 3 was prepared by the addition of 1 to a poly(phenylacetylene) containing a living end. The reaction of 2 with Mo(CO)6] produced an insoluble polymer containing Mo(CO)4(bpy)] groups, whereas with RuCl2(bpy)2] or Ru(bpy)2(CH3COCH3)2](CF3SO3)2, it gave soluble metal–polymer complexes containing Ru(bpy)3]2+ groups. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43:3167–3177, 2005 |
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| Keywords: | copolymerization 5‐ethynyl‐2 2′ ‐bipyridine metal‐polymer complexes organometallic catalysts polyacetylenes rhodium |
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