Mechanism of Unlike Stereoselectivity in 1-Alkene Primary Insertions: Syndiospecific Propene Polymerization by Brookhart-Type Nickel(II) Catalysts

Giuseppe Milano, Gaetano Guerra*, Claudio Pellecchia, Luigi Cavallo

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

29 Scopus citations

Abstract

A theoretical QM/MM study of propene polymerization by a Brookhart-type Ni(II) catalyst suggests a mechanism of unlike chain end controlled stereoselectivity for 1-alkene primary insertion. The chirality (si or re) of the tertiary carbon of the growing chain nearest to the metal determines, in the α-agostic-assisted transition state for monomer insertion, the preferential chain orientation around the metal-carbon bond (θ1 ≈ 60° or θ1 ≈ +60°, respectively). This chiral orientation of the chain, in turn, discriminates by nonbonded repulsive interactions between propene enantiofaces (re or si, respectively). Analogies and differences with respect to the well-established mechanism of chiral site controlled stereoselectivity for olefin insertion polymerizations are discussed.

Original languageEnglish (US)
Pages (from-to)1343-1349
Number of pages7
JournalOrganometallics
Volume19
Issue number7
StatePublished - Apr 3 2000

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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