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Dialkyl and Methyl-Alkyl Zirconocenes: Synthesis and Characterization of Zirconocene-Alkyls That Model the Polymeryl Chain in Alkene Polymerizations

Klamo, Sara B. and Wendt, Ola F. and Henling, Larry M. and Day, Michael W. and Bercaw, John E. (2007) Dialkyl and Methyl-Alkyl Zirconocenes: Synthesis and Characterization of Zirconocene-Alkyls That Model the Polymeryl Chain in Alkene Polymerizations. Organometallics, 26 (12). pp. 3018-3030. ISSN 0276-7333. https://resolver.caltech.edu/CaltechAUTHORS:20170308-152527539

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Abstract

Zirconocene precatalysts with sterically bulky alkyl groups were designed as model systems for the propagating species in zirconocene-catalyzed alkene polymerization. Specialty alkyllithium reagents Li(CH_2CEt_3) and Li(CH_2CMe_2CH_2Ph) were prepared and utilized in the synthesis of dialkyl and methyl-alkyl zirconocenes of the form CpCp^*ZrR_2, Cp_2Zr(CH_3)(R), and CpCp^*Zr(CH_3)(R) (Cp = (η^5-C_5H_5); Cp^* = (η^5-C_5Me_5); R = CH_2CMe_3, CH_2SiMe_3, CH_2CEt_3, CH_2CMe_2CH_2Ph). These new zirconocene alkyls were isolated and fully characterized by NMR spectroscopy and in some cases by X-ray diffraction. The molecular structures determined display the bent-sandwich coordination mode common for zirconocenes. The steric influence of the alkyl group on the observed structural parameters is reflected in slightly expanded C−Zr−C or C−Zr−Cl angles in the equatorial plane and long zirconium−alkyl bond distances.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/om0601302DOIArticle
http://pubs.acs.org/doi/full/10.1021/om0601302PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/om0601302PublisherSupporting Information
Additional Information:© 2007 American Chemical Society. Received 10 February 2006. Published online 5 May 2007. Published in print 1 June 2007. This work has been supported by USDOE Office of Basic Energy Sciences (Grant No. DE-FG03-85ER13431), Exxon Chemicals America, and the National Science Foundation (Grant No. CHE-0131180). We wish to thank Professor Thomas Livinghouse for useful suggestions in the synthesis of the specialty alkyl lithiums, David Kurtz for preparation of organic precursors, and Paul Elowe for assistance with X-ray crystallographic figures.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-FG03-85ER13431
Exxon Chemicals AmericaUNSPECIFIED
NSFCHE-0131180
Issue or Number:12
Record Number:CaltechAUTHORS:20170308-152527539
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170308-152527539
Official Citation:Dialkyl and Methyl-Alkyl Zirconocenes:  Synthesis and Characterization of Zirconocene-Alkyls That Model the Polymeryl Chain in Alkene Polymerizations Sara B. Klamo, Ola F. Wendt, Larry M. Henling, Michael W. Day, and John E. Bercaw Organometallics 2007 26 (12), 3018-3030 DOI: 10.1021/om0601302
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:74933
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:08 Mar 2017 23:41
Last Modified:03 Oct 2019 16:44

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