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. doi:10.1021/om0601302. 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.
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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. | ||||||||||||
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Issue or Number: | 12 | ||||||||||||
DOI: | 10.1021/om0601302 | ||||||||||||
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: | 15 Nov 2021 16:29 |
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