A density functional and molecular mechanics study of β-hydrogen transfer in homogeneous Ziegler-Natta catalysis

Luigi Cavallo*, Gaetano Guerra

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

74 Scopus citations


Models of catalytic complexes, of the type Cp2ZrC2H5+ and Cp2ZrC4H9+ (Cp = η5-C5H5), for the β-hydrogen transfer processes in homogeneous Ziegler-Natta polymerizations have been studied using density functional methods. We investigated the geometries and the energetics of the processes corresponding to the β-hydrogen transfer either to the metal or to the monomer. A preference for the transfer to the monomer is shown by the noticeably smaller activation barrier. The analysis has been extended through molecular mechanics calculations to models of the catalytic complexes based on the ligands BenzInd and MeBenzInd (BenzInd = (CH3)2Si(benz[e]indenyl)2 and MeBenzInd = (CH3)2Si(2-methylbenz[e]indenyl)2). This analysis, in agreement with experimental results, indicates that the β-hydrogen transfer to the monomer is more difficult in the presence of the MeBenzInd ligand due to the nonbonded interactions of the 2-methyt substituents with the C2 of both the monomer and the growing chain.

Original languageEnglish (US)
Pages (from-to)2729-2737
Number of pages9
Issue number8
StatePublished - Apr 8 1996

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

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