Bis(1,3-di-tert-butylimidazolin-2-iminato) titanium complexes as effective catalysts for the monodisperse polymerization of propylene

J Am Chem Soc. 2012 Oct 17;134(41):17234-44. doi: 10.1021/ja3071545. Epub 2012 Oct 3.

Abstract

The use of bis(1,3-di-tert-butylimidazolin-2-iminato) titanium dichloride (1) and dimethyl (2) complexes in the polymerization of propylene is presented. The complexes were activated using different amounts of methylalumoxane (MAO), giving in each case a very active catalytic mixture and producing polymers with a narrow molecular weight distribution (polydispersity = 1.10). The use of the cocatalyst triphenylcarbenium (trityl) tetra(pentafluorophenyl)borate totally inhibits the reaction, producing the corresponding bis(1,3-di-tert-butylimidazolin-2-iminato) titanium(III) methyl complex, the trityl radical ((•)CPh(3)), the anionic MeB(C(6)F(5))(4)(-), B(C(6)F(5))(3), and the bis(1,3-di-tert-butylimidazolin-2-iminato) titanium(IV) dimethyl·B(C(6)F(5))(3) complex. The use of a combination of physical methods such as NMR, ESR-C(60), and MALDI-TOF analyses enabled us to propose a plausible mechanism for the polymerization of propylene, presenting that the polymerization is mainly carried out in a living fashion. In addition, we present a slow equilibrium toward a small amount of a dormant species responsible for 2,1-misinsertions and chain transfer processes.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkenes / chemical synthesis*
  • Alkenes / chemistry
  • Catalysis
  • Models, Molecular
  • Molecular Structure
  • Organometallic Compounds / chemistry*
  • Polymerization

Substances

  • Alkenes
  • Organometallic Compounds
  • bis(1,3-di-tert-butylimidazolin-2-iminato) titanium
  • propylene