Butadiene polymerization with carbonyl and cyclopentadienyl nickel complexes combined with Lewis acids has been investigated. The microstructure of polybutadiene obtained is shown to be influenced by the nature of metal in π‐complex and independent of Lewis acid metal. In all cases polymers produced are mainly of 1,4 structure. Catalysts prepared by the reaction of nickel carbonyl with Lewis acids in aromatic hydrocarbons are arene nickel complexes. The activity of these catalysts is found to be dependent on the lability of arene–metal bond. It is suggested that there exists a genetic relation between catalyst systems studied and π‐allylic nickel complexes, which is supported by the same influence of the nature of halogen on polybutadiene microstructure.
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