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Cationic Alkylaluminum-Complexed Zirconocene Hydrides: NMR-Spectroscopic Identification, Crystallographic Structure Determination, and Interconversion with Other Zirconocene Cations

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. https://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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja1050428DOIUNSPECIFIED
http://pubs.acs.org/doi/full/10.1021/ja1050428PublisherUNSPECIFIED
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
Funders:
Funding AgencyGrant Number
Department of Energy (DOE) Office of Basic Energy SciencesDE-FG03-85ER13431
Deutsche Forschungsgemeinschaft (DFG)Bri510/14-1
Deutsche Forschungsgemeinschaft (DFG)Me1388/9-1
Fonds der Chemischen IndustrieUNSPECIFIED
BASELL Polyolefine GmbHUNSPECIFIED
NSFCHE-0639094
Issue or Number:6
Record Number:CaltechAUTHORS:20110506-141702379
Persistent URL:https://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:03 Oct 2019 02:47

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