Olefin Polymerization with Single Component Organoscandium and Organoyttrium Catalysts

  • Barbara J. Burger
  • W. Donald Cotter
  • E. Bryan Coughlin
  • Stephanie T. Chacon
  • Sharad Hajela
  • Timothy A. Herzog
  • Randolf Köhn
  • Jonathan Mitchell
  • Warren E. Piers
  • Pamela J. Shapiro
  • John E. Bercaw

Abstract

Single component catalysts for polymerization of olefins based on organoscandium and organoyttrium compounds of the types (η 5-C5Me5)2Sc-R, {(η 5-C5Me4)2SiMe2} Sc-R, meso-{(η 5-C5H3-3-CMe3)2SiMe2} Sc-R, {(η 5-C5Me4) SiMe2(η 1-NCMe3)} Sc-R, and the C 2-symmetric complexes rac-{(η 5-C5 H2-2-SiMe3-4-CMe3)2 SiMe2}Y-R (R = H, alkyl) have been prepared. All of these compounds rapidly polymerize ethylene. {(η 5-C5Me4)2SiMe2}Sc-R and meso-{(η 5-C5H3-3-CMe3)2SiMe2} Sc-R catalyze the head-to-tail dimerization of α olefins. (η 5-C5Me4)SiMe2(η 1-NCMe3)}Sc-R produces low molecular weight, essentially atactic polymers from α olefins. [rac-{(η 5-C5H2-2-SiMe3-4-CMe3) 2SiMe2}Y]2(μ-H)2 polymerizes propylene, 1-butene, 1-pentene and 1-hexene to highly isotactic, moderate molecular weight polymers. 13C NMR spectra of the polypropylene so obtained indicates greater than 99% mmmm pentads, with greater than 99.9% 1,2-insertions. The possibility that an α agostic C-H interaction is assisting olefin insertion for these catalysts has been probed using Grubbs’ test of “deuterium isotopic perturbation of stereochemistry.” Our findings implicate an a agostic structure for the transition state for chain propagation. Ground state structures for the ethyl derivatives may also have β agostic interactions. The α agostic transition state has one less rotational degree of freedom, reinforcing the enantiofacial preference of the chiral bis(cyclopentadienyl)metal site, and thus likely contributes to the high enantioselectivity of the C2-symmetricrac-{(η 5 -C5H2-2-SiMe3-4-CMe3)2 SiMe2}Y-R catalyst system.

Keywords

Zirconium Polypropylene Deuterium Yttrium Lanthanum 

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Copyright information

© Springer-Verlag Berlin Heidelberg 1995

Authors and Affiliations

  • Barbara J. Burger
    • 1
  • W. Donald Cotter
    • 1
  • E. Bryan Coughlin
    • 1
  • Stephanie T. Chacon
    • 1
  • Sharad Hajela
    • 1
  • Timothy A. Herzog
    • 1
  • Randolf Köhn
    • 1
  • Jonathan Mitchell
    • 1
  • Warren E. Piers
    • 1
  • Pamela J. Shapiro
    • 1
  • John E. Bercaw
    • 1
  1. 1.Arnold and Mabel Beckman Laboratories of Chemical SynthesisCalifornia Institute of TechnologyPasadenaUSA

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