Mechanism of isotactic styrene polymerization with a C 6F 5-substituted bis(phenoxyimine) titanium system

Lucia Caporaso, Marianna Loria, Mina Mazzeo, Kenji Michiue, Takashi Nakano, Terunori Fujita, Luigi Cavallo

Research output: Contribution to journalArticlepeer-review

11 Scopus citations


We report a combined, experimental and theoretical, study of styrene polymerization to clarify the regio- and stereocontrol mechanism operating with a C 6F 5-substituted bis(phenoxyimine) titanium dichloride complex. Styrene homopolymerization, styrene-propene and styrene-ethene-propene copolymerizations have been carried out to this aim. A combination of 13C NMR analysis of the chain-end groups and of the microstructure of the homopolymers and copolymers reveals that styrene polymerization is highly regioselective and occurs prevalently through 2,1-monomer insertion. DFT calculations evidenced that steric interaction between the growing chain and the monomer in the transition state insertion stage is at the origin of this selectivity. The formation of isotactic polystyrene with a chain-end like microstructure is rationalized on the base of a mechanism similar to that proposed for the syndiospecific propene polymerization catalyzed by bis(phenoxyimine) titanium dichloride complexes. Finally, a general stereocontrol mechanism operative in olefin polymerization with this class of complexes is proposed. © 2012 American Chemical Society.
Original languageEnglish (US)
Pages (from-to)8588-8597
Number of pages10
Issue number21
StatePublished - Oct 19 2012

ASJC Scopus subject areas

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


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