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Mechanistic Studies of Olefin and Alkyne Trimerization with Chromium Catalysts: Deuterium Labeling and Studies of Regiochemistry Using a Model Chromacyclopentane Complex

Agapie, Theodor and Labinger, Jay A. and Bercaw, John E. (2007) Mechanistic Studies of Olefin and Alkyne Trimerization with Chromium Catalysts: Deuterium Labeling and Studies of Regiochemistry Using a Model Chromacyclopentane Complex. Journal of the American Chemical Society, 129 (46). pp. 14281-14295. ISSN 0002-7863. doi:10.1021/ja073493h. https://resolver.caltech.edu/CaltechAUTHORS:20170515-111025629

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Abstract

A system for catalytic trimerization of ethylene utilizing chromium(III) precursors supported by diphosphine ligand PNP^(O4) = (o-MeO−C_6H_4)_2PN(Me)P(o-MeO−C_6H_4)_2 has been investigated. The mechanism of the olefin trimerization reaction was examined using deuterium labeling and studies of reactions with α-olefins and internal olefins. A well-defined chromium precursor utilized in this studies is Cr(PNP^(O4))(o,o‘-biphenyldiyl)Br. A cationic species, obtained by halide abstraction with NaB[C_6H_3(CF_3)_2]_4, is required for catalytic turnover to generate 1-hexene from ethylene. The initiation byproduct is vinylbiphenyl; this is formed even without activation by halide abstraction. Trimerization of 2-butyne is accomplished by the same cationic system but not by the neutral species. Catalytic trimerization, with various (PNP^(O4))Cr precursors, of a 1:1 mixture of C_2D_4 and C_2H_4 gives isotopologs 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. Using a SHOP catalyst to perform the oligomerization of a 1:1 mixture of C_2D_4 and C_2H_4 leads to the generation of a broader distribution of 1-hexene isotopologs, consistent with a Cossee-type mechanism for 1-hexene formation. The ethylene trimerization reaction was further studied by the reaction of trans-, cis-, and gem-ethylene-d_2 upon activation of Cr(PNP^(O4))(o,o‘-biphenyldiyl)Br with NaB[C_6H_3(CF_3)_2]_4. The trimerization of cis- and trans-ethylene-d_2 generates 1-hexene isotopomers having terminal CDH groups, with an isotope effect of 3.1(1) and 4.1(1), respectively. These results are consistent with reductive elimination of 1-hexene from a putative Cr(H)[(CH_2)_4CH═CH_2] occurring much faster than a hydride 2,1-insertion or with concerted 1-hexene formation from a chromacycloheptane via a 3,7-H shift. The trimerization of gem-ethylene-d2 has an isotope effect of 1.3(1), consistent with irreversible formation of a chromacycloheptane intermediate on route to 1-hexene formation. Reactions of olefins with a model of a chromacyclopentane were investigated starting from Cr(PNP^(O4))(o,o‘-biphenyldiyl)Br. α-Olefins react with cationic biphenyldiyl chromium species to generate products from 1,2-insertion. A study of the reaction of 2-butenes indicated that β-H elimination occurs preferentially from the ring CH rather than exo-CH bond in the metallacycloheptane intermediates. A study of cotrimerization of ethylene with propylene correlates with these findings of regioselectivity. Competition experiments with mixtures of two olefins indicate that the relative insertion rates generally decrease with increasing size of the olefins.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja073493hDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja073493hPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja073493hPublisherSupporting Information
ORCID:
AuthorORCID
Agapie, Theodor0000-0002-9692-7614
Labinger, Jay A.0000-0002-1942-9232
Additional Information:© 2007 American Chemical Society. Received 16 May 2007. Published online 31 October 2007. Published in print 1 November 2007. We are grateful to BP Chemicals (then Innovene) and the USDOE Office of Basic Energy Sciences (Grant No. DE-FG03-85ER13431) for financial support of this work.
Funders:
Funding AgencyGrant Number
BP ChemicalsUNSPECIFIED
Department of Energy (DOE)DE-FG03-85ER13431
Issue or Number:46
DOI:10.1021/ja073493h
Record Number:CaltechAUTHORS:20170515-111025629
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170515-111025629
Official Citation:Mechanistic Studies of Olefin and Alkyne Trimerization with Chromium Catalysts:  Deuterium Labeling and Studies of Regiochemistry Using a Model Chromacyclopentane Complex Theodor Agapie, Jay A. Labinger, and John E. Bercaw Journal of the American Chemical Society 2007 129 (46), 14281-14295 DOI: 10.1021/ja073493h
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77452
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:16 May 2017 19:41
Last Modified:15 Nov 2021 17:31

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