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Cationic Alkylaluminum-Complexed Zirconocene Hydrides as Participants in Olefin Polymerization Catalysis

Baldwin, Steven M. and Bercaw, John E. and Brintzinger, Hans H. (2010) Cationic Alkylaluminum-Complexed Zirconocene Hydrides as Participants in Olefin Polymerization Catalysis. Journal of the American Chemical Society, 132 (40). pp. 13969-13971. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20101101-101358476

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Abstract

The alkylaluminum-complexed zirconocene trihydride cation [(SBI)Zr(μ-H)_3(AliBu_2)_2]^+, which is obtained by reaction of (SBI)ZrCl_2 with [Ph_3C][B(C_6F_5)_4] and excess HAl^iBu_2 in toluene solution, catalyzes the formation of isotactic polypropene when exposed to propene at -30 °C. This cation remains the sole observable species in catalyst systems free of AlMe compounds. In the presence of AlMe_3, however, exposure to propene causes the trihydride cation to be completely converted, under concurrent consumption of all hydride species by propene hydroalumination, to the doubly Me-bridged cation [(SBI)Zr(μ-Me)_2AlMe_2]^+. The latter then becomes the resting state for further propene polymerization, which produces, by chain transfer to Al, mainly AlMe_2-capped isotactic polypropene.


Item Type:Article
Related URLs:
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http://dx.doi.org/10.1021/ja105040rDOIUNSPECIFIED
http://pubs.acs.org/doi/full/10.1021/ja105040rPublisherUNSPECIFIED
Additional Information:© 2010 American Chemical Society. Received June 9, 2010. Publication Date (Web): September 22, 2010. For GPC measurements we thank Mr. Lars Bolk (University of Konstanz). This research was supported by U.S. DOE Office of Basic Energy Sciences (Grant DE-FG03-85ER13431), Deutsche Forschungsgemeinschaft (Grants Bri510/ 14-1 and Me1388/9-1), Fonds der Chemischen Industrie, and BASELL Polyolefine GmbH.
Funders:
Funding AgencyGrant Number
Department of Energy Office of Basic Energy SciencesDE-FG03-85ER13431
Deutsche ForschungsgemeinschaftBri510/14-1
Deutsche ForschungsgemeinschaftMe1388/9-1
Fonds der Chemischen IndustrieUNSPECIFIED
BASELL Polyolefine GmbHUNSPECIFIED
Issue or Number:40
Record Number:CaltechAUTHORS:20101101-101358476
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20101101-101358476
Official Citation:Cationic Alkylaluminum-Complexed Zirconocene Hydrides as Participants in Olefin Polymerization Catalysis Steven M. Baldwin, John E. Bercaw, Hans H. Brintzinger Journal of the American Chemical Society 2010 132 (40), 13969-13971
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:20611
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:02 Nov 2010 16:39
Last Modified:03 Oct 2019 02:12

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