π‐Allyl nickel halide–oxygen system as a catalyst for polymerization of butadiene

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Abstract
The π‐allyl nickel halide‐oxygen system was found to be active as catalyst for stereospecific polymerization of butadiene. The catalyst from π‐allyl nickel chloride or π‐allyl nickel bromide yields the polymer of 90% cis‐1,4 content with high activity, whereas the catalyst from π‐allyl nickel iodide affords a polymer of 70% or less cis‐1,4 content. The catalyst systems can be fractionated into two parts on the basis of solubility in benzene. It is concluded that the catalyst activity originates essentially from the benzene‐insoluble nickel complex which is composed of oxygen, halogen, σ‐allyl group, and nickel. The structure of growing polymer terminal is discussed in relation to the mechanism of the stereospecific polymerization.
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