Chirik, Paul J. and Zubris, Deanna L. and Ackerman, Lily J. and Henling, Lawrence M. and Day, Michael W. and Bercaw, John E. (2003) Preparation of ansa-Niobocene and ansa-Tantalocene Olefin Hydride Complexes as Transition State Analogues in Metallocene-Catalyzed Olefin Polymerization. Organometallics, 22 (1). pp. 172-187. ISSN 0276-7333. doi:10.1021/om020628d. https://resolver.caltech.edu/CaltechAUTHORS:20170808-142319435
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Abstract
o examine the effects of cyclopentadienyl and olefin substitution on preferred stereochemistry, a series of singly [SiMe_2]-bridged ansa-niobocene and -tantalocene olefin hydride complexes has been prepared via reduction and alkylation of the corresponding dichloride complexes. In this manner, [Me_2Si(η^5-C_5H_4)(η^5-C_5H_3-3-R)]M(CH_2⚌CHR‘)H (M = Nb, Ta; R = CHMe_2, CMe_3; R‘ = H, C6H5; M = Ta; R = CHMe2, CMe3; R‘ = Me), rac- and meso-[Me_2Si(η^5-C_5H_3-3-R)(η^5-C_5H^3-3-R)]Nb(CH_2⚌CH_2)H (R = CMe_3), and [Me_2Si(η^5-C_5H_4)(η^5-C_5H^2-2,4-(CHMe_2)_2)]Ta(CH_2⚌CHR‘)H (R‘ = H, C_6H_5) have been prepared and characterized by NMR spectroscopy and, in some cases, X-ray diffraction. The doubly [SiMe_2]-bridged ansa-tantalocene ethylene hydride complex [(1,2-SiMe_2)_2(η^5-C_5H-3,5-(CHMe_2)_2)(η^5-C_5H_2-4-CMe_3)]Ta(CH_2⚌CH_2)H has been prepared from thermolysis of the methylidene methyl complex [(1,2-SiMe_2)_2(η^5-C_5H-3,5-(CHMe_2)_2)(η^5-C_5H_2-4-CMe_3)]Ta(CH_2)CH_3. Addition of an excess of propylene or styrene to the tantalocene ethylene hydride results in olefin exchange and formation of the olefin hydride complexes [(1,2-SiMe_2)_2(η^5-C_5H-3,5-(CHMe_2)_2)(η^5-C_5H_2-4-CMe_3)]Ta(CH_2⚌CHR‘)H (R‘ = CH_3, C_6H_5). These compounds serve as stable transition state analogues for the much more kinetically labile group 4 metallocenium cationic intermediates in metallocene-catalyzed olefin polymerization. Characterization of the thermodynamically preferred isomers of metallocene olefin hydride complexes reveals that alkyl substitution on the cyclopentadienyl ligand array may have a significant effect on the stereochemistry of olefin coordination.
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Additional Information: | © 2003 American Chemical Society. Received 2 August 2002. Published online 7 December 2002. Published in print 1 January 2003. This work has been supported by the USDOE Office of Basic Energy Sciences (Grant No. DE-FG03-85ER13431) and Exxon Chemicals America. L.J.A. wishes to thank the National Science Foundation for a Graduate Research Fellowship. | ||||||||||||
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Issue or Number: | 1 | ||||||||||||
DOI: | 10.1021/om020628d | ||||||||||||
Record Number: | CaltechAUTHORS:20170808-142319435 | ||||||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20170808-142319435 | ||||||||||||
Official Citation: | Preparation of ansa-Niobocene and ansa-Tantalocene Olefin Hydride Complexes as Transition State Analogues in Metallocene-Catalyzed Olefin Polymerization Paul J. Chirik, Deanna L. Zubris, Lily J. Ackerman, Lawrence M. Henling, Michael W. Day, and John E. Bercaw Organometallics 2003 22 (1), 172-187 DOI: 10.1021/om020628d | ||||||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||
ID Code: | 79954 | ||||||||||||
Collection: | CaltechAUTHORS | ||||||||||||
Deposited By: | Ruth Sustaita | ||||||||||||
Deposited On: | 09 Aug 2017 18:20 | ||||||||||||
Last Modified: | 15 Nov 2021 17:51 |
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