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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'-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.

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. https://doi.org/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. https://doi.org/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},
url = {https://www.osti.gov/biblio/1337683}, journal = {ACS Catalysis},
issn = {2155-5435},
number = 9,
volume = 6,
place = {United States},
year = {Tue Aug 09 00:00:00 EDT 2016},
month = {Tue Aug 09 00:00:00 EDT 2016}
}

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Cited by: 80 works
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Works referenced in this record:

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Understanding the CO Oxidation on Pt Nanoparticles Supported on MOFs by Operando XPS
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Polymer-Supported Palladium(II) Carbene Complexes: Catalytic Activity, Recyclability, and Selectivity in C−H Acetoxylation of Arenes
journal, May 2017


A novel modified MIL-101-NH 2 ligand for CuI-catalyzed and air promoted oxidation of secondary alcohols
journal, January 2017


Rational Design of Catalytic Centers in Crystalline Frameworks
journal, June 2018


Fast and Selective Semihydrogenation of Alkynes by Palladium Nanoparticles Sandwiched in Metal–Organic Frameworks
journal, January 2020


Single Pt Atoms Confined into a Metal-Organic Framework for Efficient Photocatalysis
journal, January 2018


Fast and Selective Semihydrogenation of Alkynes by Palladium Nanoparticles Sandwiched in Metal–Organic Frameworks
journal, January 2020