Agapie, Theodor and Schofer, Susan J. and Labinger, Jay A. and Bercaw, John E. (2004) Mechanistic Studies of the Ethylene Trimerization Reaction with Chromium−Diphosphine Catalysts: Experimental Evidence for a Mechanism Involving Metallacyclic Intermediates. Journal of the American Chemical Society, 126 (5). pp. 1304-1305. ISSN 0002-7863. doi:10.1021/ja038968t. https://resolver.caltech.edu/CaltechAUTHORS:20170419-145525386
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Abstract
A system for catalytic trimerization of ethylene utilizing CrCl_3(THF)_3 and a diphosphine ligand PNP^(OMe) [= (o-MeO-C_6H_4)_2PN(Me)P(o-MeO-C_6H_4)_2] has been investigated. The coordination chemistry of chromium with PNP^(OMe) has been explored, and (PNP^(OMe))CrCl_3 and (PNP^(OMe))CrPh_3 (3) have been synthesized by ether displacement from chromium(III) precursors. Salt metathesis of (PNP^(OMe))CrCl_3 with o,o‘-biphenyldiyl Grignard affords (PNP^(OMe))Cr(o,o‘-biphenyldiyl)Br (4). Activation of 3 with H(Et_2O)_2B[C_6H_3(CF_3)_2]_4 or 4 with NaB[C_6H_3(CF_3)_2]_4 generates a catalytic system and trimerizes a 1:1 mixture of C_2D_4 and C_2H_4 to give isotopomers of 1-hexene without H/D scrambling (C_6D_(12), C_6D_8H_4, C_6D_4H_8, and C_6H_(12) in a 1:3:3:1 ratio). The lack of crossover supports a mechanism involving metallacyclic intermediates. The mechanism of the ethylene trimerization reaction has also been studied by the reaction of trans-, cis-, and gem-ethylene-d_2 with 4 upon activation with NaB[C_6H_3(CF_3)_2]_4.
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Additional Information: | © 2004 American Chemical Society. Received 9 October 2003. Published online 15 January 2004. Published in print 1 February 2004. We thank Drs. Steven A. Cohen, Glenn Sunley, and Duncan F. Wass (BP) for helpful discussions and Michael W. Day and Lawrence M. Henling (Caltech) for assistance with single-crystal X-ray crystallographic studies. We are grateful to BP Chemicals for financial support. | ||||||||||||
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Issue or Number: | 5 | ||||||||||||
DOI: | 10.1021/ja038968t | ||||||||||||
Record Number: | CaltechAUTHORS:20170419-145525386 | ||||||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20170419-145525386 | ||||||||||||
Official Citation: | Mechanistic Studies of the Ethylene Trimerization Reaction with Chromium−Diphosphine Catalysts: Experimental Evidence for a Mechanism Involving Metallacyclic Intermediates Theodor Agapie, Susan J. Schofer, Jay A. Labinger, and John E. Bercaw Journal of the American Chemical Society 2004 126 (5), 1304-1305 DOI: 10.1021/ja038968t | ||||||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||
ID Code: | 76714 | ||||||||||||
Collection: | CaltechAUTHORS | ||||||||||||
Deposited By: | Ruth Sustaita | ||||||||||||
Deposited On: | 20 Apr 2017 14:35 | ||||||||||||
Last Modified: | 15 Nov 2021 17:02 |
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