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A Chromium-Diphosphine System for Catalytic Ethylene Trimerization: Synthetic and Structural Studies of Chromium Complexes with a Nitrogen-Bridged Diphosphine Ligand with ortho-Methoxyaryl Substituents

Agapie, Theodor and Day, Michael W. and Henling, Lawrence M. and Labinger, Jay A. and Bercaw, John E. (2006) A Chromium-Diphosphine System for Catalytic Ethylene Trimerization: Synthetic and Structural Studies of Chromium Complexes with a Nitrogen-Bridged Diphosphine Ligand with ortho-Methoxyaryl Substituents. Organometallics, 25 (11). pp. 2733-2742. ISSN 0276-7333. https://resolver.caltech.edu/CaltechAUTHORS:20170726-082000200

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Abstract

To gain molecular-level insight into the important features of a chromium-diphosphine catalytic system for ethylene trimerization, the coordination chemistry of chromium with “PNP” ligands (PNP^(OMe) = (o-MeOC_6H_4)_2PN(CH_3)P(o-MeOC_6H_4)_2, P^(t-Bu)N^(i-amyl)P_(OMe)) = (2-MeO-4-t-BuC_6H_3)_2PN(i-amyl)P(2-MeO-4-t-BuC_6H_3)_2) has been explored. Chromium(0) carbonyl complexes have been synthesized by CO displacement with diphosphine. Oxidation of Cr(CO)_4{κ^2-(P,P)-(PNP^(OMe))} with I_2, Br_2, and PhICl_2 generates the corresponding chromium(III) halide complexes. Chromium(III) complexes CrCl_3{(κ^3-(P,P,O)-(PNP^(OMe))}, CrCl_3{κ^3-(P,P,O)-(P^(t-)^(Bu)N^(i-amyl)P^(OMe))}, and CrCl_2(CH_3){κ^3-(P,P,O)-(PNP^(OMe))} can be synthesized by metalation with CrCl_3(THF)_3 or CrCl_2(CH_3)(THF)_3. Reaction of CrCl_3{κ^3-(P,P,O)-(PNP^(OMe))} with o,o‘-biphenyldiyl diGrignard affords CrBr(o,o‘-biphenyldiyl){κ^3-(P,P,O)-(PNP^(OMe))}. Single-crystal X-ray diffraction studies show that the Cr−O and Cr−P distances can vary significantly as a function of metal oxidation state and the other ligands bound to chromium. Variable-temperature ^2H NMR spectroscopy studies of chromium(III) complexes supported by PNP ligands indicate fluxional behavior with the ether groups interchanging at higher temperatures. Low-temperature ^2H NMR spectra are consistent with solution structures similar to the ones determined in the solid state.


Item Type:Article
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URLURL TypeDescription
http://dx.doi.org/10.1021/om050605+DOIArticle
http://pubs.acs.org/doi/abs/10.1021/om050605%2BPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/om050605%2BPublisherSupporting Information
ORCID:
AuthorORCID
Agapie, Theodor0000-0002-9692-7614
Labinger, Jay A.0000-0002-1942-9232
Additional Information:© 2006 American Chemical Society. Received 19 July 2005. Published online 28 April 2006. Published in print 1 May 2006. We thank Dr. Steven A. Cohen for helpful discussions. We are grateful to BP Chemicals (now Innovene) for financial support.
Funders:
Funding AgencyGrant Number
BP ChemicalsUNSPECIFIED
Issue or Number:11
Record Number:CaltechAUTHORS:20170726-082000200
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170726-082000200
Official Citation:A Chromium-Diphosphine System for Catalytic Ethylene Trimerization:  Synthetic and Structural Studies of Chromium Complexes with a Nitrogen-Bridged Diphosphine Ligand with ortho-Methoxyaryl Substituents Theodor Agapie, Michael W. Day, Lawrence M. Henling, Jay A. Labinger, and John E. Bercaw Organometallics 2006 25 (11), 2733-2742 DOI: 10.1021/om050605+
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:79387
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:26 Jul 2017 15:56
Last Modified:03 Oct 2019 18:19

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