Unveiling the Effects of Linker Substitution in Suzuki Coupling with Palladium Nanoparticles in Metal–Organic Frameworks [Unveiling the Effects of Linker Substitution in Suzuki Coupling Reaction with Palladium Nanoparticles in Metal–Organic Frameworks]
Abstract
The establishment of structure–property relationships in heterogeneous catalysis is of prime importance but remains a formidable challenge. Metal–organic frameworks (MOFs) featuring excellent chemical tunability are emerging as an auspicious platform for the atomic-level control of heterogeneous catalysis. Herein, we encapsulate palladium nanoparticles (Pd NPs) in a series of isoreticular mixed-linker MOFs, and the obtained MOF-Pd NPs catalysts were used to unveil the electronic and steric effects of linker substitution on the activity of these catalysts in the Suzuki–Miyaura cross-coupling reactions. Significantly, m-6,6'-Me2bpy-MOF-Pd exhibits a remarkable enhancement in the activity compared to non-functionalized m-bpy-MOF-Pd and m-4,4'-Me2bpy-MOF-Pd. This study unambiguously demonstrates that the stereoelectronic properties of linker units are crucial to the catalytic activity of nanoparticles encapsulated in MOFs. More interestingly, the trend of activity change is consistent with our previous work on catalytic sites generated in situ from Pd(II) coordinated in MOFs bearing the same functional groups, which suggests that both MOF-Pd NPs and MOF-Pd(II) catalysts generate similar active centers during Suzuki–Miyaura coupling reactions. Lastly, this work paves a new avenue to the fabrication of advanced and tunable MOF-based catalysts through rational linker engineering.
- Authors:
-
- Ames Lab. and Iowa State Univ., Ames, IA (United States)
- Iowa State Univ., Ames, IA (United States)
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1434313
- Report Number(s):
- IS-J-9636
Journal ID: ISSN 1011-372X; PII: 2289
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Catalysis Letters
- Additional Journal Information:
- Journal Volume: 148; Journal Issue: 3; Journal ID: ISSN 1011-372X
- Publisher:
- Springer
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Isoreticular metal–organic frameworks; Heterogeneous catalysis; Suzuki–Miyaura cross-coupling; Structure–activity relationship
Citation Formats
Li, Xinle, Zhang, Biying, Van Zeeland, Ryan, Tang, Linlin, Pei, Yuchen, Qi, Zhiyuan, Goh, Tian Wei, Stanley, Levi M., and Huang, Wenyu. Unveiling the Effects of Linker Substitution in Suzuki Coupling with Palladium Nanoparticles in Metal–Organic Frameworks [Unveiling the Effects of Linker Substitution in Suzuki Coupling Reaction with Palladium Nanoparticles in Metal–Organic Frameworks]. United States: N. p., 2018.
Web. doi:10.1007/s10562-017-2289-9.
Li, Xinle, Zhang, Biying, Van Zeeland, Ryan, Tang, Linlin, Pei, Yuchen, Qi, Zhiyuan, Goh, Tian Wei, Stanley, Levi M., & Huang, Wenyu. Unveiling the Effects of Linker Substitution in Suzuki Coupling with Palladium Nanoparticles in Metal–Organic Frameworks [Unveiling the Effects of Linker Substitution in Suzuki Coupling Reaction with Palladium Nanoparticles in Metal–Organic Frameworks]. United States. https://doi.org/10.1007/s10562-017-2289-9
Li, Xinle, Zhang, Biying, Van Zeeland, Ryan, Tang, Linlin, Pei, Yuchen, Qi, Zhiyuan, Goh, Tian Wei, Stanley, Levi M., and Huang, Wenyu. Thu .
"Unveiling the Effects of Linker Substitution in Suzuki Coupling with Palladium Nanoparticles in Metal–Organic Frameworks [Unveiling the Effects of Linker Substitution in Suzuki Coupling Reaction with Palladium Nanoparticles in Metal–Organic Frameworks]". United States. https://doi.org/10.1007/s10562-017-2289-9. https://www.osti.gov/servlets/purl/1434313.
@article{osti_1434313,
title = {Unveiling the Effects of Linker Substitution in Suzuki Coupling with Palladium Nanoparticles in Metal–Organic Frameworks [Unveiling the Effects of Linker Substitution in Suzuki Coupling Reaction with Palladium Nanoparticles in Metal–Organic Frameworks]},
author = {Li, Xinle and Zhang, Biying and Van Zeeland, Ryan and Tang, Linlin and Pei, Yuchen and Qi, Zhiyuan and Goh, Tian Wei and Stanley, Levi M. and Huang, Wenyu},
abstractNote = {The establishment of structure–property relationships in heterogeneous catalysis is of prime importance but remains a formidable challenge. Metal–organic frameworks (MOFs) featuring excellent chemical tunability are emerging as an auspicious platform for the atomic-level control of heterogeneous catalysis. Herein, we encapsulate palladium nanoparticles (Pd NPs) in a series of isoreticular mixed-linker MOFs, and the obtained MOF-Pd NPs catalysts were used to unveil the electronic and steric effects of linker substitution on the activity of these catalysts in the Suzuki–Miyaura cross-coupling reactions. Significantly, m-6,6'-Me2bpy-MOF-Pd exhibits a remarkable enhancement in the activity compared to non-functionalized m-bpy-MOF-Pd and m-4,4'-Me2bpy-MOF-Pd. This study unambiguously demonstrates that the stereoelectronic properties of linker units are crucial to the catalytic activity of nanoparticles encapsulated in MOFs. More interestingly, the trend of activity change is consistent with our previous work on catalytic sites generated in situ from Pd(II) coordinated in MOFs bearing the same functional groups, which suggests that both MOF-Pd NPs and MOF-Pd(II) catalysts generate similar active centers during Suzuki–Miyaura coupling reactions. Lastly, this work paves a new avenue to the fabrication of advanced and tunable MOF-based catalysts through rational linker engineering.},
doi = {10.1007/s10562-017-2289-9},
journal = {Catalysis Letters},
number = 3,
volume = 148,
place = {United States},
year = {Thu Jan 18 00:00:00 EST 2018},
month = {Thu Jan 18 00:00:00 EST 2018}
}
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Cited by: 18 works
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Figures / Tables:
Scheme 1: Schematic representation of the synthesis of Pd NPs encapsulated in isoreticular mbpy- MOFs. Green sphere and octahedra represent Zr clusters, while orange spheres represent Pd NPs.
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Works referenced in this record:
Metal–organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations
journal, January 2015
- Chughtai, Adeel H.; Ahmad, Nazir; Younus, Hussein A.
- Chemical Society Reviews, Vol. 44, Issue 19
Catalysis by metal nanoparticles embedded on metal–organic frameworks
journal, January 2012
- Dhakshinamoorthy, Amarajothi; Garcia, Hermenegildo
- Chemical Society Reviews, Vol. 41, Issue 15
Chemical Environment Control and Enhanced Catalytic Performance of Platinum Nanoparticles Embedded in Nanocrystalline Metal–Organic Frameworks
journal, June 2015
- Choi, Kyung Min; Na, Kyungsu; Somorjai, Gabor A.
- Journal of the American Chemical Society, Vol. 137, Issue 24
Postsynthetic Metalation of Bipyridyl-Containing Metal–Organic Frameworks for Highly Efficient Catalytic Organic Transformations
journal, April 2014
- Manna, Kuntal; Zhang, Teng; Lin, Wenbin
- Journal of the American Chemical Society, Vol. 136, Issue 18
Postsynthetic Ligand and Cation Exchange in Robust Metal–Organic Frameworks
journal, October 2012
- Kim, Min; Cahill, John F.; Fei, Honghan
- Journal of the American Chemical Society, Vol. 134, Issue 43
Facile preparation of Pd nanoparticles supported on single-layer graphene oxide and application for the Suzuki–Miyaura cross-coupling reaction
journal, January 2014
- Yamamoto, Shun-ichi; Kinoshita, Hiroshi; Hashimoto, Hideki
- Nanoscale, Vol. 6, Issue 12
Sustainable Catalysis: Rational Pd Loading on MIL-101Cr-NH 2 for More Efficient and Recyclable Suzuki-Miyaura Reactions
journal, November 2013
- Pascanu, Vlad; Yao, Qingxia; Bermejo Gómez, Antonio
- Chemistry - A European Journal, Vol. 19, Issue 51
Molecular Encapsulation beyond the Aperture Size Limit through Dissociative Linker Exchange in Metal–Organic Framework Crystals
journal, August 2014
- Morabito, Joseph V.; Chou, Lien-Yang; Li, Zhehui
- Journal of the American Chemical Society, Vol. 136, Issue 36
Heterogeneous Suzuki reactions catalyzed by Pd(0)–Y zeolite
journal, May 2004
- Artok, Levent; Bulut, Hatice
- Tetrahedron Letters, Vol. 45, Issue 20
The Use of Palladium on Magnetic Support as Catalyst for Suzuki–Miyaura Cross-Coupling Reactions
journal, January 2017
- Sydnes, Magne
- Catalysts, Vol. 7, Issue 12
Interrogating the catalytic mechanism of nanoparticle mediated Stille coupling reactions employing bio-inspired Pd nanocatalysts
journal, January 2011
- Pacardo, Dennis B.; Slocik, Joseph M.; Kirk, Kyle C.
- Nanoscale, Vol. 3, Issue 5
Phosphine-stabilized Pd nanoparticles supported on silica as a highly active catalyst for the Suzuki–Miyaura cross-coupling reaction
journal, January 2015
- Sahu, Debojeet; Das, Pankaj
- RSC Advances, Vol. 5, Issue 5
Controlling Catalytic Properties of Pd Nanoclusters through Their Chemical Environment at the Atomic Level Using Isoreticular Metal–Organic Frameworks
journal, April 2016
- Li, Xinle; Goh, Tian Wei; Li, Lei
- ACS Catalysis, Vol. 6, Issue 6
Immobilization of Pd(II) on MOFs as a highly active heterogeneous catalyst for Suzuki–Miyaura and Ullmann-type coupling reactions
journal, May 2015
- Chen, Liyu; Gao, Zhiqiang; Li, Yingwei
- Catalysis Today, Vol. 245
Mechanical properties of hybrid inorganic–organic framework materials: establishing fundamental structure–property relationships
journal, January 2011
- Tan, Jin Chong; Cheetham, Anthony K.
- Chemical Society Reviews, Vol. 40, Issue 2
Chitosan-based heterogeneous catalysts for Suzuki and Heck reactions
journal, January 2004
- Hardy, Jeff J. E.; Hubert, Sandrine; Macquarrie, Duncan J.
- Green Chemistry, Vol. 6, Issue 1
Water Stability and Adsorption in Metal–Organic Frameworks
journal, September 2014
- Burtch, Nicholas C.; Jasuja, Himanshu; Walton, Krista S.
- Chemical Reviews, Vol. 114, Issue 20, p. 10575-10612
On the Nature of the Active Species in Palladium Catalyzed Mizoroki–Heck and Suzuki–Miyaura Couplings – Homogeneous or Heterogeneous Catalysis, A Critical Review
journal, April 2006
- Phan, Nam T. S.; Van Der Sluys, Matthew; Jones, Christopher W.
- Advanced Synthesis & Catalysis, Vol. 348, Issue 6
Magnesium Nanocrystals Embedded in a Metal-Organic Framework: Hybrid Hydrogen Storage with Synergistic Effect on Physi- and Chemisorption
journal, September 2012
- Lim, Dae-Woon; Yoon, Ji Woong; Ryu, Keun Yong
- Angewandte Chemie, Vol. 124, Issue 39
Utilizing mixed-linker zirconium based metal-organic frameworks to enhance the visible light photocatalytic oxidation of alcohol
journal, March 2015
- Goh, Tian Wei; Xiao, Chaoxian; Maligal-Ganesh, Raghu V.
- Chemical Engineering Science, Vol. 124
Highly Functionalized Biaryls via Suzuki-Miyaura Cross-Coupling Catalyzed by Pd@MOF under Batch and Continuous Flow Regimes
journal, November 2014
- Pascanu, Vlad; Hansen, Peter R.; Bermejo Gómez, Antonio
- ChemSusChem, Vol. 8, Issue 1
A Highly Active Heterogeneous Palladium Catalyst for the Suzuki-Miyaura and Ullmann Coupling Reactions of Aryl Chlorides in Aqueous Media
journal, April 2010
- Yuan, Bizhen; Pan, Yingyi; Li, Yingwei
- Angewandte Chemie International Edition, Vol. 49, Issue 24
Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis
journal, November 2002
- Kotha, Sambasivarao; Lahiri, Kakali; Kashinath, Dhurke
- Tetrahedron, Vol. 58, Issue 48
Engineering the Optical Response of the Titanium-MIL-125 Metal–Organic Framework through Ligand Functionalization
journal, July 2013
- Hendon, Christopher H.; Tiana, Davide; Fontecave, Marc
- Journal of the American Chemical Society, Vol. 135, Issue 30
Unexpected activation of carbon–bromide bond promoted by palladium nanoparticles in Suzuki C–C couplings
journal, January 2010
- Sanhes, Delphine; Raluy, Eva; Rétory, Stéphane
- Dalton Transactions, Vol. 39, Issue 40
Heterogeneous Pd/C-Catalyzed Ligand-Free, Room-Temperature Suzuki–Miyaura Coupling Reactions in Aqueous Media
journal, July 2007
- Maegawa, Tomohiro; Kitamura, Yoshiaki; Sako, Satoko
- Chemistry - A European Journal, Vol. 13, Issue 20
A molecular Pd( ii ) complex incorporated into a MOF as a highly active single-site heterogeneous catalyst for C–Cl bond activation
journal, January 2014
- Chen, Liyu; Rangan, Sylvie; Li, Jing
- Green Chemistry, Vol. 16, Issue 8
Anchoring of Palladium onto Surface of Porous Metal–Organic Framework through Post-Synthesis Modification and Studies on Suzuki and Stille Coupling Reactions under Heterogeneous Condition
journal, February 2013
- Saha, Debraj; Sen, Rupam; Maity, Tanmoy
- Langmuir, Vol. 29, Issue 9
Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal-Organic Frameworks
journal, April 2012
- Vermoortele, Frederik; Vandichel, Matthias; Van de Voorde, Ben
- Angewandte Chemie International Edition, Vol. 51, Issue 20
Influence of Connectivity and Porosity on Ligand-Based Luminescence in Zinc Metal−Organic Frameworks
journal, June 2007
- Bauer, Christina A.; Timofeeva, Tatiana V.; Settersten, Thomas B.
- Journal of the American Chemical Society, Vol. 129, Issue 22
Influence of the Base on Pd@MIL-101-NH 2 (Cr) as Catalyst for the Suzuki-Miyaura Cross-Coupling Reaction
journal, June 2015
- Carson , Fabian; Pascanu , Vlad; Bermejo Gómez , Antonio
- Chemistry - A European Journal, Vol. 21, Issue 30
Palladium Nanoparticles as Efficient Green Homogeneous and Heterogeneous Carbon−Carbon Coupling Precatalysts: A Unifying View
journal, March 2007
- Astruc, Didier
- Inorganic Chemistry, Vol. 46, Issue 6
Impact of Linker Engineering on the Catalytic Activity of Metal–Organic Frameworks Containing Pd(II)–Bipyridine Complexes
journal, August 2016
- Li, Xinle; Van Zeeland, Ryan; Maligal-Ganesh, Raghu V.
- ACS Catalysis, Vol. 6, Issue 9
The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013
- Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
- Science, Vol. 341, Issue 6149, p. 1230444-1230444
Metal−organic framework encapsulated Pd nanoparticles: towards advanced heterogeneous catalysts
journal, January 2014
- Chen, Liyu; Chen, Huirong; Luque, Rafael
- Chem. Sci., Vol. 5, Issue 10
Tandem Catalysis by Palladium Nanoclusters Encapsulated in Metal–Organic Frameworks
journal, September 2014
- Li, Xinle; Guo, Zhiyong; Xiao, Chaoxian
- ACS Catalysis, Vol. 4, Issue 10
Pd nanoparticles for C–C coupling reactions
journal, January 2011
- Balanta, Angelica; Godard, Cyril; Claver, Carmen
- Chemical Society Reviews, Vol. 40, Issue 10
Mechanism of a Suzuki-Type Homocoupling Reaction Catalyzed by Palladium Nanocubes
journal, January 2017
- Elias, Welman C.; Signori, Aline M.; Zaramello, Laize
- ACS Catalysis, Vol. 7, Issue 2
A Highly Active Heterogeneous Palladium Catalyst for the Suzuki-Miyaura and Ullmann Coupling Reactions of Aryl Chlorides in Aqueous Media
journal, April 2010
- Yuan, Bizhen; Pan, Yingyi; Li, Yingwei
- Angewandte Chemie, Vol. 122, Issue 24
Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal-Organic Frameworks
journal, April 2012
- Vermoortele, Frederik; Vandichel, Matthias; Van de Voorde, Ben
- Angewandte Chemie, Vol. 124, Issue 20
Recent Applications of the Suzuki—Miyaura Cross-Coupling Reaction in Organic Synthesis
journal, March 2003
- Kotha, Sambasivarao; Lahiri, Kakali; Kashinath, Dhurke
- ChemInform, Vol. 34, Issue 9
Heterogeneous Suzuki Reactions Catalyzed by Pd(0)—Y Zeolite.
journal, August 2004
- Artok, Levent; Bulut, Hatice
- ChemInform, Vol. 35, Issue 35
Magnesium Nanocrystals Embedded in a Metal-Organic Framework: Hybrid Hydrogen Storage with Synergistic Effect on Physi- and Chemisorption
journal, September 2012
- Lim, Dae-Woon; Yoon, Ji Woong; Ryu, Keun Yong
- Angewandte Chemie International Edition, Vol. 51, Issue 39
Works referencing / citing this record:
1,10‐Phenanthroline Carboxylic Acids for Preparation of Functionalized Metal‐Organic Frameworks
journal, September 2019
- Abel, Anton S.; Yu Mitrofanov, Alexander; Yakushev, Aleksei A.
- Asian Journal of Organic Chemistry, Vol. 8, Issue 11
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