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Title: Impact of linker engineering on the catalytic activity of metal–organic frameworks containing Pd(II)–bipyridine complexes

Abstract

A series of mixed-linker bipyridyl metal–organic framework (MOF)-supported palladium(II) catalysts were used to elucidate the electronic and steric effects of linker substitution on the activity of these catalysts in the context of Suzuki–Miyaura cross-coupling reactions. m-6,6'-Me 2bpy-MOF-PdCl 2 exhibited 110- and 496-fold enhancements in activity compared to nonfunctionalized m-bpy-MOF-PdCl 2 and m-4,4'-Me 2bpy-MOF-PdCl 2, respectively. Furthermore, this result clearly demonstrates that the stereoelectronic properties of metal-binding linker units are critical to the activity of single-site organometallic catalysts in MOFs and highlights the importance of linker engineering in the design and development of efficient MOF catalysts.

Authors:
 [1];  [2];  [1];  [1];  [2];  [2];  [1]
  1. Iowa State Univ., Ames, IA (United States); Ames Lab., Ames, IA (United States)
  2. Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1337683
Report Number(s):
IS-J-9087
Journal ID: ISSN 2155-5435
Grant/Contract Number:
AC02-07CH11358
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 9; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; bipyridyl linker; heterogeneous catalysis; isoreticular metal−organic frameworks; single-site catalyst; structure−activity relationship; Suzuki−Miyaura cross-coupling

Citation Formats

Li, Xinle, Van Zeeland, Ryan, Maligal-Ganesh, Raghu V., Pei, Yuchen, Power, Gregory, Stanley, Levi, and Huang, Wenyu. Impact of linker engineering on the catalytic activity of metal–organic frameworks containing Pd(II)–bipyridine complexes. United States: N. p., 2016. Web. doi:10.1021/acscatal.6b01753.
Li, Xinle, Van Zeeland, Ryan, Maligal-Ganesh, Raghu V., Pei, Yuchen, Power, Gregory, Stanley, Levi, & Huang, Wenyu. Impact of linker engineering on the catalytic activity of metal–organic frameworks containing Pd(II)–bipyridine complexes. United States. doi:10.1021/acscatal.6b01753.
Li, Xinle, Van Zeeland, Ryan, Maligal-Ganesh, Raghu V., Pei, Yuchen, Power, Gregory, Stanley, Levi, and Huang, Wenyu. 2016. "Impact of linker engineering on the catalytic activity of metal–organic frameworks containing Pd(II)–bipyridine complexes". United States. doi:10.1021/acscatal.6b01753. https://www.osti.gov/servlets/purl/1337683.
@article{osti_1337683,
title = {Impact of linker engineering on the catalytic activity of metal–organic frameworks containing Pd(II)–bipyridine complexes},
author = {Li, Xinle and Van Zeeland, Ryan and Maligal-Ganesh, Raghu V. and Pei, Yuchen and Power, Gregory and Stanley, Levi and Huang, Wenyu},
abstractNote = {A series of mixed-linker bipyridyl metal–organic framework (MOF)-supported palladium(II) catalysts were used to elucidate the electronic and steric effects of linker substitution on the activity of these catalysts in the context of Suzuki–Miyaura cross-coupling reactions. m-6,6'-Me2bpy-MOF-PdCl2 exhibited 110- and 496-fold enhancements in activity compared to nonfunctionalized m-bpy-MOF-PdCl2 and m-4,4'-Me2bpy-MOF-PdCl2, respectively. Furthermore, this result clearly demonstrates that the stereoelectronic properties of metal-binding linker units are critical to the activity of single-site organometallic catalysts in MOFs and highlights the importance of linker engineering in the design and development of efficient MOF catalysts.},
doi = {10.1021/acscatal.6b01753},
journal = {ACS Catalysis},
number = 9,
volume = 6,
place = {United States},
year = 2016,
month = 8
}

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Cited by: 6works
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  • We report here the synthesis of a series of robust and porous bipyridyl- and phenanthryl-based metal–organic frameworks (MOFs) of UiO topology (BPV-MOF, mBPV-MOF, and mPT-MOF) and their postsynthetic metalation to afford highly active single-site solid catalysts. While BPV-MOF was constructed from only bipyridyl-functionalized dicarboxylate linker, both mBPV- and mPT-MOF were built with a mixture of bipyridyl- or phenanthryl-functionalized and unfunctionalized dicarboxylate linkers. The postsynthetic metalation of these MOFs with [Ir(COD)(OMe)] 2 provided Ir-functionalized MOFs (BPV-MOF-Ir, mBPV-MOF-Ir, and mPT-MOF-Ir), which are highly active catalysts for tandem hydrosilylation of aryl ketones and aldehydes followed by dehydrogenative ortho-silylation of benzylicsilyl ethers as wellmore » as C–H borylation of arenes using B₂pin₂. Both mBPV-MOF-Ir and mPT-MOF-Ir catalysts displayed superior activities compared to BPV-MOF-Ir due to the presence of larger open channels in the mixed-linker MOFs. Impressively, mBPV-MOF-Ir exhibited high TONs of up to 17000 for C–H borylation reactions and was recycled more than 15 times. The mPT-MOF-Ir system is also active in catalyzing tandem dehydrosilylation/dehydrogenative cyclization of N-methylbenzyl amines to azasilolanes in the absence of a hydrogen acceptor. Importantly, MOF-Ir catalysts are significantly more active (up to 95 times) and stable than their homogeneous counterparts for all three reactions, strongly supporting the beneficial effects of active site isolation within MOFs. This work illustrates the ability to increase MOF open channel sizes by using the mixed linker approach and shows the enormous potential of developing highly active and robust single-site solid catalysts based on MOFs containing nitrogen-donor ligands for important organic transformations.« less
  • Mono(phosphine)–M (M–PR3; M = Rh and Ir) complexes selectively prepared by postsynthetic metalation of a porous triarylphosphine-based metal–organic framework (MOF) exhibited excellent activity in the hydrosilylation of ketones and alkenes, the hydrogenation of alkenes, and the C–H borylation of arenes. The recyclable and reusable MOF catalysts significantly outperformed their homogeneous counterparts, presumably via stabilizing M–PR3 intermediates by preventing deleterious disproportionation reactions/ligand exchanges in the catalytic cycles.
  • Iron metal–organic frameworks (MOFs) [Fe(L){sub 2}(SCN){sub 2}]{sub ∝} (L1: 4-bpdh=2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene for 1Fe; and L2: 3-bpdh=2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene for 2Fe) were assembled in a MeOH–H{sub 2}O solvent system. 1Fe exhibits a two-dimensional extended-grid network, whereas 2Fe exhibits a stair-like double-chain; the N-position within the pyridine ring of the complexes was observed to regulate the MOF structure as layers or chains. Furthermore, selectively catalytic activity was observed for the layered MOF but not the chain-structured MOF; micro/nanoparticles of the layered MOF were therefore investigated for new potential applications of micro/nano MOFs. - Graphical abstract: Iron metal–organic frameworks (MOFs) [Fe(L){sub 2}(SCN){sub 2}]{sub ∝} (L1: 4-bpdh=2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadienemore » for 1Fe; and L2: 3-bpdh=2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene for 2Fe) were assembled in a MeOH–H{sub 2}O solvent system. The N-position within the pyridine ring of the complexes was observed to regulate the MOF structure as layers or chains. Selectively catalytic activity was observed for the layered MOF but not the chain-structured MOF. - Highlights: • Synthesis and structure of metal–organic framework [Fe(L){sub 2}(SCN){sub 2}]{sub ∝}. • Selectively catalytic activity depending on the N-position within the pyridine ring. • The degradation and conversion of methyl orange.« less