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Title: Ethylene oligomerization in metal–organic frameworks bearing nickel(ii) 2,2'-bipyridine complexes

Abstract

Here, the metal–organic frameworks Zr 6O 4(OH) 4(bpydc) 6(1; bpydc 2–= 2,2'-bipyridine-5,5'-dicarboxylate) and Zr 6O 4(OH) 4(bpydc) 0.84(bpdc) 5.16(2; bpdc 21458983 = biphenyl-4,4'-dicarboxylate) were readily metalated with Ni(DME)Br 2(DME = dimethoxyethane) to produce the corresponding metalated frameworks1(NiBr 2) 6and2(NiBr 2) 0.84. Both nickel(ii)-containing frameworks catalyze the oligomerization of ethylene in the presence of Et 2AlCl. In these systems, the pore environment around the active nickel sites significantly influences their selectivity for formation of oligomers over polymer. Specifically, the single-crystal structure of1(NiBr 2) 5.64reveals that surrounding metal–linker complexes enforce a steric environment on each nickel site that causes polymer formation to become favorable. Minimizing this steric congestion by isolating the nickel(ii) bipyridine complexes in the mixed-linker framework2(NiBr 2) 0.84markedly improves both the catalytic activity and selectivity for oligomers. Furthermore, both frameworks give product mixtures that are enriched in shorter olefins (C 4–10), leading to deviations from the expected Schulz–Flory distribution of oligomers. Although these deviations indicate possible pore confinement effects on selectivity, control experiments using the nickel-treated biphenyl framework Zr 6O 4(OH) 4(bpdc) 6(NiBr 2) 0.14(3(NiBr 2) 0.14) reveal that they likely arise at least in part from the presence of nickel species that are not ligated by bipyridine within1(NiBr 2)more » 5.64and2(NiBr 2) 0.84.« less

Authors:
 [1];  [1]; ORCiD logo [2]
  1. Univ. of California, Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1458983
Grant/Contract Number:  
FG02-12ER16362; SC0008688
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Faraday Discussions
Additional Journal Information:
Journal Volume: 201; Journal ID: ISSN 1359-6640
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gonzalez, Miguel I., Oktawiec, Julia, and Long, Jeffrey R. Ethylene oligomerization in metal–organic frameworks bearing nickel(ii) 2,2'-bipyridine complexes. United States: N. p., 2017. Web. doi:10.1039/C7FD00061H.
Gonzalez, Miguel I., Oktawiec, Julia, & Long, Jeffrey R. Ethylene oligomerization in metal–organic frameworks bearing nickel(ii) 2,2'-bipyridine complexes. United States. doi:10.1039/C7FD00061H.
Gonzalez, Miguel I., Oktawiec, Julia, and Long, Jeffrey R. Wed . "Ethylene oligomerization in metal–organic frameworks bearing nickel(ii) 2,2'-bipyridine complexes". United States. doi:10.1039/C7FD00061H. https://www.osti.gov/servlets/purl/1458983.
@article{osti_1458983,
title = {Ethylene oligomerization in metal–organic frameworks bearing nickel(ii) 2,2'-bipyridine complexes},
author = {Gonzalez, Miguel I. and Oktawiec, Julia and Long, Jeffrey R.},
abstractNote = {Here, the metal–organic frameworks Zr6O4(OH)4(bpydc)6(1; bpydc2–= 2,2'-bipyridine-5,5'-dicarboxylate) and Zr6O4(OH)4(bpydc)0.84(bpdc)5.16(2; bpdc21458983 = biphenyl-4,4'-dicarboxylate) were readily metalated with Ni(DME)Br2(DME = dimethoxyethane) to produce the corresponding metalated frameworks1(NiBr2)6and2(NiBr2)0.84. Both nickel(ii)-containing frameworks catalyze the oligomerization of ethylene in the presence of Et2AlCl. In these systems, the pore environment around the active nickel sites significantly influences their selectivity for formation of oligomers over polymer. Specifically, the single-crystal structure of1(NiBr2)5.64reveals that surrounding metal–linker complexes enforce a steric environment on each nickel site that causes polymer formation to become favorable. Minimizing this steric congestion by isolating the nickel(ii) bipyridine complexes in the mixed-linker framework2(NiBr2)0.84markedly improves both the catalytic activity and selectivity for oligomers. Furthermore, both frameworks give product mixtures that are enriched in shorter olefins (C4–10), leading to deviations from the expected Schulz–Flory distribution of oligomers. Although these deviations indicate possible pore confinement effects on selectivity, control experiments using the nickel-treated biphenyl framework Zr6O4(OH)4(bpdc)6(NiBr2)0.14(3(NiBr2)0.14) reveal that they likely arise at least in part from the presence of nickel species that are not ligated by bipyridine within1(NiBr2)5.64and2(NiBr2)0.84.},
doi = {10.1039/C7FD00061H},
journal = {Faraday Discussions},
issn = {1359-6640},
number = ,
volume = 201,
place = {United States},
year = {2017},
month = {2}
}

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Cited by: 12 works
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Figures / Tables:

Figure 1 Figure 1: A portion of the crystal structure of Zr6O4(OH)4(bpydc)6(NiBr2)5.64 at 100 K as determined by analysis of single crystal X-ray diffraction data; yellow, green, dark red, red, blue, and gray spheres represent Zr, Ni, Br, O, N, and C atoms, respectively. The NiII centers are disordered over two positionsmore » (Figure S1), but are represented here in only one orientation. Coordinated solvent molecules that complete the NiII coordination sphere could not be modeled due to disorder and weak scattering compared to the Br ligands. Hydrogen atoms are omitted for clarity.« less

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    Works referencing / citing this record:

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    journal, October 2015

    • Yuan, Shuai; Chen, Ying-Pin; Qin, Junsheng
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    • DOI: 10.1002/ange.201505625

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    Oligomerization of Ethylene to α-Olefins: Discovery and Development of the Shell Higher Olefin Process (SHOP)
    journal, October 2013


    Definitive Molecular Level Characterization of Defects in UiO-66 Crystals
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    • Trickett, Christopher A.; Gagnon, Kevin J.; Lee, Seungkyu
    • Angewandte Chemie International Edition, Vol. 54, Issue 38
    • DOI: 10.1002/anie.201505461

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    • Rama, Gustavo; Ardá, Ana; Maréchal, Jean-Didier
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    • Helldörfer, Markus; Milius, Wolfgang; Alt, Helmut G.
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    • DOI: 10.1016/s1381-1169(02)00519-8

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    journal, May 2016


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    Toward “metalloMOFzymes”: Metal–Organic Frameworks with Single-Site Metal Catalysts for Small-Molecule Transformations
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    Gas-Phase Dimerization of Ethylene under Mild Conditions Catalyzed by MOF Materials Containing (bpy)Ni II Complexes
    journal, October 2015

    • Madrahimov, Sherzod T.; Gallagher, James R.; Zhang, Guanghui
    • ACS Catalysis, Vol. 5, Issue 11
    • DOI: 10.1021/acscatal.5b01604

    Ethylene Oligomerization beyond Schulz–Flory Distributions
    journal, October 2015

    • Britovsek, George J. P.; Malinowski, Robert; McGuinness, David S.
    • ACS Catalysis, Vol. 5, Issue 11
    • DOI: 10.1021/acscatal.5b02203

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    Catalytic Ethylene Dimerization and Oligomerization:  Recent Developments with Nickel Complexes Containing P , N-Chelating Ligands
    journal, October 2005

    • Speiser, Fredy; Braunstein, Pierre; Saussine, Lucien
    • Accounts of Chemical Research, Vol. 38, Issue 10
    • DOI: 10.1021/ar050040d

    Tuned to Perfection: Ironing Out the Defects in Metal–Organic Framework UiO-66
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    • Shearer, Greig C.; Chavan, Sachin; Ethiraj, Jayashree
    • Chemistry of Materials, Vol. 26, Issue 14
    • DOI: 10.1021/cm501859p

    Olefin Oligomerization via Metallacycles: Dimerization, Trimerization, Tetramerization, and Beyond
    journal, March 2011


    Late-Metal Catalysts for Ethylene Homo- and Copolymerization
    journal, April 2000

    • Ittel, Steven D.; Johnson, Lynda K.; Brookhart, Maurice
    • Chemical Reviews, Vol. 100, Issue 4
    • DOI: 10.1021/cr9804644

    Selective Propene Oligomerization with Nickel(II)-Based Metal–Organic Frameworks
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    • Mlinar, Anton N.; Keitz, Benjamin K.; Gygi, David
    • ACS Catalysis, Vol. 4, Issue 3
    • DOI: 10.1021/cs401189a

    New Pd(II)- and Ni(II)-Based Catalysts for Polymerization of Ethylene and .alpha.-Olefins
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    • Johnson, Lynda K.; Killian, Christopher M.; Brookhart, Maurice
    • Journal of the American Chemical Society, Vol. 117, Issue 23
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    Computational Study of the Effect of Confinement within Microporous Structures on the Activity and Selectivity of Metallocene Catalysts for Ethylene Oligomerization
    journal, March 2011

    • Toulhoat, Hervé; Lontsi Fomena, Mireille; de Bruin, Theodorus
    • Journal of the American Chemical Society, Vol. 133, Issue 8
    • DOI: 10.1021/ja105950z

    MOF-Supported Selective Ethylene Dimerization Single-Site Catalysts through One-Pot Postsynthetic Modification
    journal, March 2013

    • Canivet, Jerome; Aguado, Sonia; Schuurman, Yves
    • Journal of the American Chemical Society, Vol. 135, Issue 11
    • DOI: 10.1021/ja312120x

    Postsynthetic Metalation of Bipyridyl-Containing Metal–Organic Frameworks for Highly Efficient Catalytic Organic Transformations
    journal, April 2014

    • Manna, Kuntal; Zhang, Teng; Lin, Wenbin
    • Journal of the American Chemical Society, Vol. 136, Issue 18
    • DOI: 10.1021/ja5018267

    Salicylaldimine-Based Metal–Organic Framework Enabling Highly Active Olefin Hydrogenation with Iron and Cobalt Catalysts
    journal, September 2014

    • Manna, Kuntal; Zhang, Teng; Carboni, Michaël
    • Journal of the American Chemical Society, Vol. 136, Issue 38
    • DOI: 10.1021/ja507947d

    Bipyridine- and Phenanthroline-Based Metal–Organic Frameworks for Highly Efficient and Tandem Catalytic Organic Transformations via Directed C–H Activation
    journal, February 2015

    • Manna, Kuntal; Zhang, Teng; Greene, Francis X.
    • Journal of the American Chemical Society, Vol. 137, Issue 7
    • DOI: 10.1021/ja512478y

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    Metal–Organic Frameworks Stabilize Solution-Inaccessible Cobalt Catalysts for Highly Efficient Broad-Scope Organic Transformations
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    Metal–Organic Framework Nodes Support Single-Site Magnesium–Alkyl Catalysts for Hydroboration and Hydroamination Reactions
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    Pore Environment Effects on Catalytic Cyclohexane Oxidation in Expanded Fe 2 (dobdc) Analogues
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    Indexing of powder diffraction patterns by iterative use of singular value decomposition
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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.