Baldwin, Steven M. and Bercaw, John E. and Henling, Lawrence M. and Day, Michael W. and Brintzinger, Hans 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). pp. 1805-1813. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20110506-141702379
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Abstract
The ansa-zirconocene complex rac-Me_2Si(1-indenyl)_2ZrCl_2 ((SBI)ZrCl_2) reacts with diisobutylaluminum hydride and trityl tetrakis(perfluorophenyl)borate in hydrocarbon solutions to give the cation [(SBI)Zr(μ-H)_3(Al^iBu_2)_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(Al^iBu2)_2]^+ reacts reversibly with ClAl^iBu_2 to give the dichloro-bridged cation [(SBI)Zr(μ-Cl)_2Al^iBu_2]^+. Reaction with AlMe_3 first leads to mixed-alkyl species [(SBI)Zr(μ-H)_3(AlMe_x^iBu_(2−x))_2^]+ by exchange of alkyl groups between aluminum centers. At higher AlMe_3/Zr ratios, [(SBI)Zr(μ-Me)_2AlMe_2]^+, a constituent of methylalumoxane-activated catalyst systems, is formed in an equilibrium, in which the hydride cation [(SBI)Zr(μ-H)_3(AlR_2)_2]^+ strongly predominates at comparable HAl^iBu_2 and AlMe_3 concentrations, thus implicating the presence of this hydride cation in olefin polymerization catalyst systems.
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| Additional Information: | © 2011 American Chemical Society. Received: June 9, 2010. Published: January 18, 2011. This research was supported by the US DOE Office of Basic Energy Sciences (Grant DE-FG03-85ER13431), by the Deutsche Forschungsgemeinschaft (Grants Bri510/14-1 and Me1388/9-1), by Fonds der Chemischen Industrie, and by BASELL Polyolefine GmbH. The X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology, CHE-0639094 | ||||||||||||||
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| Record Number: | CaltechAUTHORS:20110506-141702379 | ||||||||||||||
| Persistent URL: | http://resolver.caltech.edu/CaltechAUTHORS:20110506-141702379 | ||||||||||||||
| Official Citation: | Cationic Alkylaluminum-Complexed Zirconocene Hydrides: NMR-Spectroscopic Identification, Crystallographic Structure Determination, and Interconversion with Other Zirconocene Cations Steven M. Baldwin, John E. Bercaw, Lawrence M. Henling, Michael W. Day, Hans H. Brintzinger Journal of the American Chemical Society 2011 133 (6), 1805-1813 | ||||||||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||||
| ID Code: | 23590 | ||||||||||||||
| Collection: | CaltechAUTHORS | ||||||||||||||
| Deposited By: | Ruth Sustaita | ||||||||||||||
| Deposited On: | 09 May 2011 17:31 | ||||||||||||||
| Last Modified: | 28 Mar 2014 04:13 |
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