Organoactinides in the polymerization of ethylene: is TIBA a better cocatalyst than MAO?

Dalton Trans. 2013 Jul 7;42(25):9069-78. doi: 10.1039/c3dt00032j. Epub 2013 Apr 10.

Abstract

The synthesis of two pyridylamidinate bis(N,N'-bis(trimethylsilyl)-2-pyridylamidinate)An(μ-Cl)2Li(TMEDA) (An = U (1), Th (2)) complexes is presented. For complex 1 the solid state X-ray structures were studied and compared to that of complex 2. The organoactinide complexes were studied as pre-catalysts in the polymerization of ethylene when activated by methylalumoxane (MAO). The catalytic activity was improved using a mixture of trityl tetrakispentafluorophenylborate (TTPB) and a small amount of methylalumoxane (MAO) as cocatalysts, and was amazingly improved, providing the greatest activity, using only triisobutyl aluminum (TIBA). We present a combination of ESR, C60 radical trapping, and MALDI-TOF studies describing the formation of the single-site active species, capturing some unique features of the complexes and shedding light on the polymerization mechanism.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Actinoid Series Elements / chemistry*
  • Catalysis
  • Ethylenes / chemistry*
  • Lithium / chemistry*
  • Models, Molecular
  • Molecular Structure
  • Organometallic Compounds / chemical synthesis*
  • Organometallic Compounds / chemistry
  • Polymerization
  • Uranium / chemistry*

Substances

  • Actinoid Series Elements
  • Ethylenes
  • Organometallic Compounds
  • triisobutylaluminum
  • Uranium
  • ethylene
  • Lithium