Abstract
AbstractNovel nickelocene‐based catalysts were used for polymerization of diphenylacetylene and phenylacetylene. The catalyst obtained in the reaction of nickelocene with organolithium compounds in the presence of alkyne was previously isolated and fully characterized. This enabled us to explain the mechanism of the polymerization. Polymerization of alkynes proceeds according to a coordination–insertion mechanism. Coordinated acetylene molecule inserts into an NiC bond. An active catalytic species of polymerization appeared to be {CpNiR} stabilized by alkyne molecule. Cyclization is catalyzed by {CpNiH} species. The mechanism of polymerization and cyclization reaction was determined based on the composition of the reaction products formed, gel‐permeation chromatography and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry measurements. Copyright © 2004 John Wiley & Sons, Ltd.
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