Ethylene oligomerization in metal–organic frameworks bearing nickel(ii) 2,2'-bipyridine complexes
Abstract
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.
- Authors:
-
[2]
- Univ. of California, Berkeley, CA (United States)
- 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:
- 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},
journal = {Faraday Discussions},
number = ,
volume = 201,
place = {United States},
year = {Wed Feb 22 00:00:00 EST 2017},
month = {Wed Feb 22 00:00:00 EST 2017}
}
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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 »
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