skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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) (SC-22)
OSTI Identifier:
1458983
Grant/Contract Number:  
FG02-12ER16362; SC0008688
Resource Type:
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},
number = ,
volume = 201,
place = {United States},
year = {2017},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

A short history of SHELX
journal, December 2007

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
  • DOI: 10.1107/S0108767307043930

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

  • Cavka, Jasmina Hafizovic; Jakobsen, S�ren; Olsbye, Unni
  • Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851
  • DOI: 10.1021/ja8057953

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


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

  • Spek, Anthony L.
  • Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 9-18
  • DOI: 10.1107/S2053229614024929

    Works referencing / citing this record: