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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. https://doi.org/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. https://doi.org/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},
url = {https://www.osti.gov/biblio/1458983}, 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 Zr 6O 4(OH) 4(bpydc) 6(NiBr 2) 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 NiIImore » centers are disordered over two positions (Figure S1), but are represented here in only one orientation. Coordinated solvent molecules that complete the Ni II 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 referenced in this record:

Sintering-Resistant Single-Site Nickel Catalyst Supported by Metal–Organic Framework
journal, February 2016


Gas-Phase Dimerization of Ethylene under Mild Conditions Catalyzed by MOF Materials Containing (bpy)Ni II Complexes
journal, October 2015


Mechanism of Single-Site Molecule-Like Catalytic Ethylene Dimerization in Ni-MFU-4 l
journal, January 2017


Advances in selective ethylene trimerisation – a critical overview
journal, November 2004


Post-synthetic metalation of metal–organic frameworks
journal, January 2014


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


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


Selective Dimerization of Ethylene to 1-Butene with a Porous Catalyst
journal, February 2016


Preparation of Linear α-Olefins Using Cationic Nickel(II) α-Diimine Catalysts
journal, May 1997


Oxidation of ethane to ethanol by N2O in a metal–organic framework with coordinatively unsaturated iron(II) sites
journal, May 2014


Toward “metalloMOFzymes”: Metal–Organic Frameworks with Single-Site Metal Catalysts for Small-Molecule Transformations
journal, May 2016


Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks
journal, October 2015


Defect Engineering: Tuning the Porosity and Composition of the Metal–Organic Framework UiO-66 via Modulated Synthesis
journal, May 2016


Nickel: An Element with Wide Application in Industrial Homogeneous Catalysis
journal, March 1990


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


Stereoselective Formation of Chiral Metallopeptides
journal, May 2012


OLEX2 : a complete structure solution, refinement and analysis program
journal, January 2009


Single-Crystal-to-Single-Crystal Metalation of a Metal–Organic Framework: A Route toward Structurally Well-Defined Catalysts
journal, February 2015


Definitive Molecular Level Characterization of Defects in UiO-66 Crystals
journal, August 2015


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


New processes for the selective production of 1-octene
journal, July 2011


Iron-Based Catalysts with Exceptionally High Activities and Selectivities for Oligomerization of Ethylene to Linear α-Olefins
journal, July 1998


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


Ethylene Oligomerization and Propylene Dimerization Using Cationic (α-Diimine)nickel(II) Catalysts
journal, January 1999


A short history of SHELX
journal, December 2007


Processes for the production of higher linear α-olefins
journal, July 2010


Metal–Organic Frameworks Stabilize Solution-Inaccessible Cobalt Catalysts for Highly Efficient Broad-Scope Organic Transformations
journal, February 2016


Ethylene Oligomerization beyond Schulz–Flory Distributions
journal, October 2015


New Pd(II)- and Ni(II)-Based Catalysts for Polymerization of Ethylene and .alpha.-Olefins
journal, June 1995


Four-coordinated bipyridine complexes of nickel for ethene polymerization—the role of ligand structure
journal, November 2000


Computational Study of the Effect of Confinement within Microporous Structures on the Activity and Selectivity of Metallocene Catalysts for Ethylene Oligomerization
journal, March 2011


Pore Environment Effects on Catalytic Cyclohexane Oxidation in Expanded Fe 2 (dobdc) Analogues
journal, October 2016


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


A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability
journal, October 2008

  • Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni
  • Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851
  • https://doi.org/10.1021/ja8057953

Photocatalytic CO 2 Reduction to Formate Using a Mn(I) Molecular Catalyst in a Robust Metal–Organic Framework
journal, July 2015


Metal–Organic Framework Nodes Support Single-Site Magnesium–Alkyl Catalysts for Hydroboration and Hydroamination Reactions
journal, June 2016


Tuned to Perfection: Ironing Out the Defects in Metal–Organic Framework UiO-66
journal, July 2014


Single-crystal structure validation with the program PLATON
journal, January 2003


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


Postsynthetic modification of mixed-linker metal–organic frameworks for ethylene oligomerization
journal, January 2014


Selective Propene Oligomerization with Nickel(II)-Based Metal–Organic Frameworks
journal, January 2014


Nickel-based solid catalysts for ethylene oligomerization – a review
journal, January 2014


Indexing of powder diffraction patterns by iterative use of singular value decomposition
journal, January 2003


Striking different behavior in the activation of α-olefins by homogeneous and heterogenized catalysts based on η5-cyclopentadienyl nickel derivatives
journal, September 1996


Oligomerization of Monoolefins by Homogeneous Catalysts
journal, September 2009


PLATON SQUEEZE: a tool for the calculation of the disordered solvent contribution to the calculated structure factors
journal, January 2015


A robust, catalytic metal–organic framework with open 2,2′-bipyridine sites
journal, January 2014


Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks
journal, October 2015


    Works referencing / citing this record:

    Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks
    journal, October 2015


    Nickel: An Element with Wide Application in Industrial Homogeneous Catalysis
    journal, March 1990


    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
    journal, August 2015


    Stereoselective Formation of Chiral Metallopeptides
    journal, May 2012


    Striking different behavior in the activation of α-olefins by homogeneous and heterogenized catalysts based on η5-cyclopentadienyl nickel derivatives
    journal, September 1996


    New processes for the selective production of 1-octene
    journal, July 2011


    Advances in selective ethylene trimerisation – a critical overview
    journal, November 2004


    Four-coordinated bipyridine complexes of nickel for ethene polymerization—the role of ligand structure
    journal, November 2000


    Defect Engineering: Tuning the Porosity and Composition of the Metal–Organic Framework UiO-66 via Modulated Synthesis
    journal, May 2016


    Single-Crystal-to-Single-Crystal Metalation of a Metal–Organic Framework: A Route toward Structurally Well-Defined Catalysts
    journal, February 2015


    Photocatalytic CO 2 Reduction to Formate Using a Mn(I) Molecular Catalyst in a Robust Metal–Organic Framework
    journal, July 2015


    Toward “metalloMOFzymes”: Metal–Organic Frameworks with Single-Site Metal Catalysts for Small-Molecule Transformations
    journal, May 2016


    Gas-Phase Dimerization of Ethylene under Mild Conditions Catalyzed by MOF Materials Containing (bpy)Ni II Complexes
    journal, October 2015


    Ethylene Oligomerization beyond Schulz–Flory Distributions
    journal, October 2015


    Selective Dimerization of Ethylene to 1-Butene with a Porous Catalyst
    journal, February 2016


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


    Tuned to Perfection: Ironing Out the Defects in Metal–Organic Framework UiO-66
    journal, July 2014


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


    Selective Propene Oligomerization with Nickel(II)-Based Metal–Organic Frameworks
    journal, January 2014


    New Pd(II)- and Ni(II)-Based Catalysts for Polymerization of Ethylene and .alpha.-Olefins
    journal, June 1995


    Computational Study of the Effect of Confinement within Microporous Structures on the Activity and Selectivity of Metallocene Catalysts for Ethylene Oligomerization
    journal, March 2011


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


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


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


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


    A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability
    journal, October 2008

    • Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni
    • Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851
    • https://doi.org/10.1021/ja8057953

    Iron-Based Catalysts with Exceptionally High Activities and Selectivities for Oligomerization of Ethylene to Linear α-Olefins
    journal, July 1998


    Sintering-Resistant Single-Site Nickel Catalyst Supported by Metal–Organic Framework
    journal, February 2016


    Metal–Organic Frameworks Stabilize Solution-Inaccessible Cobalt Catalysts for Highly Efficient Broad-Scope Organic Transformations
    journal, February 2016


    Metal–Organic Framework Nodes Support Single-Site Magnesium–Alkyl Catalysts for Hydroboration and Hydroamination Reactions
    journal, June 2016


    Pore Environment Effects on Catalytic Cyclohexane Oxidation in Expanded Fe 2 (dobdc) Analogues
    journal, October 2016


    Mechanism of Single-Site Molecule-Like Catalytic Ethylene Dimerization in Ni-MFU-4 l
    journal, January 2017


    Preparation of Linear α-Olefins Using Cationic Nickel(II) α-Diimine Catalysts
    journal, May 1997


    Ethylene Oligomerization and Propylene Dimerization Using Cationic (α-Diimine)nickel(II) Catalysts
    journal, January 1999


    Oxidation of ethane to ethanol by N2O in a metal–organic framework with coordinatively unsaturated iron(II) sites
    journal, May 2014


    A robust, catalytic metal–organic framework with open 2,2′-bipyridine sites
    journal, January 2014


    Post-synthetic metalation of metal–organic frameworks
    journal, January 2014


    Nickel-based solid catalysts for ethylene oligomerization – a review
    journal, January 2014


    Postsynthetic modification of mixed-linker metal–organic frameworks for ethylene oligomerization
    journal, January 2014


    Indexing of powder diffraction patterns by iterative use of singular value decomposition
    journal, January 2003


    Single-crystal structure validation with the program PLATON
    journal, January 2003


    OLEX2 : a complete structure solution, refinement and analysis program
    journal, January 2009


    A short history of SHELX
    journal, December 2007


    PLATON SQUEEZE: a tool for the calculation of the disordered solvent contribution to the calculated structure factors
    journal, January 2015


    Processes for the production of higher linear α-olefins
    journal, July 2010


    Oligomerization of Monoolefins by Homogeneous Catalysts
    journal, September 2009


    Microporous Polymers as Macroligands for Pentamethylcyclopentadienylrhodium Transfer-Hydrogenation Catalysts
    journal, February 2018


    Gas reactions under intrapore condensation regime within tailored metal–organic framework catalysts
    journal, May 2019


    Operando study of palladium nanoparticles inside UiO-67 MOF for catalytic hydrogenation of hydrocarbons
    journal, January 2018


    Influence of nanoscale structuralisation on the catalytic performance of ZIF-8: a cautionary surface catalysis study
    journal, January 2018


    Towards highly active and stable nickel-based metal–organic frameworks as ethylene oligomerization catalysts
    journal, January 2019


      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.