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Alkylaluminum-complexed zirconocene hydrides: Identification of hydride-bridged species by NMR spectroscopy

Publication ,  Journal Article
Baldwin, SM; Bereaw, JE; Brintzinger, HH
Published in: Journal of the American Chemical Society
December 24, 2008

Reactions of unbridged zirconocene dichlorides, (R nC 5H 5-n) 2ZrCl 2 (n=0, 1, or 2), with diisobutylaluminum hydride (HAI'Bu 2) result in the formation of tetranuclear trihydride clusters of the type (R nC 5H 5-n) 2Zr(μ-H) 3(Al iBu2)3(μ-CI) 2, which contain three [Al iBu 2] units. Ring-bridged ansa-zirconocene dichlorides, Me2E(R nC 5H 4-n) 2ZrCl 2 with E=C or Si, on the other hand, are found to form binuclear dihydride complexes of the type Me2E(R nC 5H 4-n) 2Zr(CI)(μ-H) 2Al iBu 2 with only one [AIBu 2] unit. The dichotomy between unbridged and bridged zirconocene derivatives with regard to tetranuclear versus binuclear product formation is proposed to be connected to different degrees of rotational freedom of their C 5-ring ligands. Alkylaluminum-complexed zirconocene dihydrides, previously observed in zirconocene-based precatalyst systems activated by methylalumoxane (MAO) upon addition of HAI'Bu 2 or Al iBu 3, are proposed to be species of the type Me 2Si(ind) 2Zr(Me)(μ-H) 2Al iBu 2, stabilized by interaction of their terminal Me group with a Lewis acidic site of MAO. © 2008 American Chemical Society.

Duke Scholars

Published In

Journal of the American Chemical Society

DOI

ISSN

0002-7863

Publication Date

December 24, 2008

Volume

130

Issue

51

Start / End Page

17423 / 17433

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences
 

Citation

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Baldwin, S. M., Bereaw, J. E., & Brintzinger, H. H. (2008). Alkylaluminum-complexed zirconocene hydrides: Identification of hydride-bridged species by NMR spectroscopy. Journal of the American Chemical Society, 130(51), 17423–17433. https://doi.org/10.1021/ja8054723
Baldwin, S. M., J. E. Bereaw, and H. H. Brintzinger. “Alkylaluminum-complexed zirconocene hydrides: Identification of hydride-bridged species by NMR spectroscopy.” Journal of the American Chemical Society 130, no. 51 (December 24, 2008): 17423–33. https://doi.org/10.1021/ja8054723.
Baldwin SM, Bereaw JE, Brintzinger HH. Alkylaluminum-complexed zirconocene hydrides: Identification of hydride-bridged species by NMR spectroscopy. Journal of the American Chemical Society. 2008 Dec 24;130(51):17423–33.
Baldwin, S. M., et al. “Alkylaluminum-complexed zirconocene hydrides: Identification of hydride-bridged species by NMR spectroscopy.” Journal of the American Chemical Society, vol. 130, no. 51, Dec. 2008, pp. 17423–33. Scopus, doi:10.1021/ja8054723.
Baldwin SM, Bereaw JE, Brintzinger HH. Alkylaluminum-complexed zirconocene hydrides: Identification of hydride-bridged species by NMR spectroscopy. Journal of the American Chemical Society. 2008 Dec 24;130(51):17423–17433.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

ISSN

0002-7863

Publication Date

December 24, 2008

Volume

130

Issue

51

Start / End Page

17423 / 17433

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences