Key interactions in heterogeneous Ziegler-Natta catalytic systems: Structure and energetics of TiCL4-lewis base complexes

Luigi Cavallo*, Silvia Del Piero, Jean Marie Ducéré, Rosalisa Fedele, Andrea Melchior, Giampiero Morini, Fabrizio Piemontesi, Marilena Tolazzi

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

64 Scopus citations


Extensive calorimetric investigations on the interaction of TiCl 4 with some Lewis bases are presented. Some of the bases were chosen for their industrial relevance in heterogeneous Ziegler-Natta polymerization of propene (ethyl benzoate, L2, diisobutyl phthalate, L3, (2S,3S)-diethyl 2,3-diisopropylsuccinate, L6, (2S,35)-diethyl 2,3-diisopropylsuccinate, L7, and 9,9-bis(methoxymethyl)-9H-fluorene, L13) while other bases were chosen as probe molecules to explore the electronic and steric effects on the complexation energy (ethyl acetate, L1, diethyl phthalate, L4, diethyl succinate, L5, tetrahydrofuran, L8, dimethoxyethane, L9, dimethoxypropane, L10, dimethoxybutane, L11, and 3,3-bis(methoxymethyl)-2,6-dimethylheptane, L12). 1,1,2,2,-Tetrachloroethane was selected as the solvent for its low donating properties, which allows the focus to be on the metal-donor interaction. The calorimetric data are discussed and compared with the efficiency of the derived catalysts. Further understanding is obtained by comparison of the experimental results with theoretical calculations based on density functional theory (DFT). The performance of different computational approaches was validated by comparison of the calculated and experimental complexation energies.

Original languageEnglish (US)
Pages (from-to)4412-4419
Number of pages8
JournalJournal of Physical Chemistry C
Issue number11
StatePublished - Mar 22 2007

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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