Skip to main content
Journal cover image

Cationic alkylaluminum-complexed zirconocene hydrides: NMR-spectroscopic identification, crystallographic structure determination, and interconversion with other zirconocene cations

Publication ,  Journal Article
Baldwin, SM; Bercaw, JE; Henling, LM; Day, MW; Brintzinger, HH
Published in: Journal of the American Chemical Society
2011

The ansa-zirconocene complex rac-Me2Si(1-indenyl) 2ZrCl2 ((SBI)ZrCl2) reacts with diisobutylaluminum hydride and trityl tetrakis(perfluorophenyl)borate in hydrocarbon solutions to give the cation [(SBI)Zr(μ-H)3(Al iBu2)2]+, the identity of which is derived from NMR data and supported by a crystallographic structure determination. Analogous reactions proceed with many other zirconocene dichloride complexes. [(SBI)Zr(μ-H)3(AliBu 2)2]+ reacts reversibly with ClAl iBu2 to give the dichloro-bridged cation [(SBI)Zr(μ-Cl)2AliBu2]+. Reaction with AlMe3 first leads to mixed-alkyl species [(SBI)Zr(μ-H) 3(AlMexiBu2-x)2] + by exchange of alkyl groups between aluminum centers. At higher AlMe3/Zr ratios, [(SBI)Zr(μ-Me)2AlMe2] +, a constituent of methylalumoxane-activated catalyst systems, is formed in an equilibrium, in which the hydride cation [(SBI)Zr(μ-H) 3(AlR2)2]+ strongly predominates at comparable HAliBu2 and AlMe3 concentrations, thus implicating the presence of this hydride cation in olefin polymerization catalyst systems. © 2011 American Chemical Society.

Duke Scholars

Published In

Journal of the American Chemical Society

DOI

ISSN

0002-7863

Publication Date

2011

Volume

133

Issue

6

Start / End Page

1805 / 1813

Related Subject Headings

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

Citation

APA
Chicago
ICMJE
MLA
NLM
Baldwin, S. M., Bercaw, J. E., Henling, L. M., Day, M. W., & Brintzinger, H. H. (2011). Cationic alkylaluminum-complexed zirconocene hydrides: NMR-spectroscopic identification, crystallographic structure determination, and interconversion with other zirconocene cations. Journal of the American Chemical Society, 133(6), 1805–1813. https://doi.org/10.1021/ja1050428
Baldwin, S. M., J. E. Bercaw, L. M. Henling, M. W. Day, and H. H. Brintzinger. “Cationic alkylaluminum-complexed zirconocene hydrides: NMR-spectroscopic identification, crystallographic structure determination, and interconversion with other zirconocene cations.” Journal of the American Chemical Society 133, no. 6 (2011): 1805–13. https://doi.org/10.1021/ja1050428.
Baldwin SM, Bercaw JE, Henling LM, Day MW, Brintzinger HH. Cationic alkylaluminum-complexed zirconocene hydrides: NMR-spectroscopic identification, crystallographic structure determination, and interconversion with other zirconocene cations. Journal of the American Chemical Society. 2011;133(6):1805–13.
Baldwin, S. M., et al. “Cationic alkylaluminum-complexed zirconocene hydrides: NMR-spectroscopic identification, crystallographic structure determination, and interconversion with other zirconocene cations.” Journal of the American Chemical Society, vol. 133, no. 6, 2011, pp. 1805–13. Scival, doi:10.1021/ja1050428.
Baldwin SM, Bercaw JE, Henling LM, Day MW, Brintzinger HH. Cationic alkylaluminum-complexed zirconocene hydrides: NMR-spectroscopic identification, crystallographic structure determination, and interconversion with other zirconocene cations. Journal of the American Chemical Society. 2011;133(6):1805–1813.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

ISSN

0002-7863

Publication Date

2011

Volume

133

Issue

6

Start / End Page

1805 / 1813

Related Subject Headings

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