CaltechAUTHORS
  A Caltech Library Service

Mechanistic Studies of the Ethylene Trimerization Reaction with Chromium−Diphosphine Catalysts: Experimental Evidence for a Mechanism Involving Metallacyclic Intermediates

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

[img] Crystallographic Info File (CIF) - Supplemental Material
See Usage Policy.

97kB
[img] PDF - Supplemental Material
See Usage Policy.

3MB

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20170419-145525386

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja038968tDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja038968tPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja038968tPublisherSupporting Information
ORCID:
AuthorORCID
Agapie, Theodor0000-0002-9692-7614
Labinger, Jay A.0000-0002-1942-9232
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.
Funders:
Funding AgencyGrant Number
BP ChemicalsUNSPECIFIED
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

Repository Staff Only: item control page