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]

Li, Xinle; Zhang, Biying; Van Zeeland, Ryan; Tang, Linlin; Pei, Yuchen; Qi, Zhiyuan; Goh, Tian Wei; Stanley, Levi M.; Huang, Wenyu

doi:10.1007/s10562-017-2289-9

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]

Journal Article · Thu Jan 18 00:00:00 EST 2018 · Catalysis Letters

DOI:https://doi.org/10.1007/s10562-017-2289-9· OSTI ID:1434313

Li, Xinle ^[1]; Zhang, Biying ^[1]; Van Zeeland, Ryan ^[2]; Tang, Linlin ^[2]; Pei, Yuchen ^[1]; Qi, Zhiyuan ^[1]; Goh, Tian Wei ^[1]; Stanley, Levi M. ^[2]; Huang, Wenyu ^[1]

Ames Lab. and Iowa State Univ., Ames, IA (United States)
Iowa State Univ., Ames, IA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1434313

Report Number(s):: IS-J--9636; PII: 2289

Journal Information:: Catalysis Letters, Journal Name: Catalysis Letters Journal Issue: 3 Vol. 148; ISSN 1011-372X

Publisher:: SpringerCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

On the Nature of the Active Species in Palladium Catalyzed Mizoroki–Heck and Suzuki–Miyaura Couplings – Homogeneous or Heterogeneous Catalysis, A Critical Review Phan, Nam T. S.; Van Der Sluys, Matthew; Jones, Christopher W. Advanced Synthesis & Catalysis, Vol. 348, Issue 6 https://doi.org/10.1002/adsc.200505473	journal	April 2006
A Highly Active Heterogeneous Palladium Catalyst for the Suzuki-Miyaura and Ullmann Coupling Reactions of Aryl Chlorides in Aqueous Media Yuan, Bizhen; Pan, Yingyi; Li, Yingwei Angewandte Chemie, Vol. 122, Issue 24 https://doi.org/10.1002/ange.201000576	journal	April 2010
Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal-Organic Frameworks Vermoortele, Frederik; Vandichel, Matthias; Van de Voorde, Ben Angewandte Chemie, Vol. 124, Issue 20 https://doi.org/10.1002/ange.201108565	journal	April 2012
Magnesium Nanocrystals Embedded in a Metal-Organic Framework: Hybrid Hydrogen Storage with Synergistic Effect on Physi- and Chemisorption Lim, Dae-Woon; Yoon, Ji Woong; Ryu, Keun Yong Angewandte Chemie, Vol. 124, Issue 39 https://doi.org/10.1002/ange.201206055	journal	September 2012
A Highly Active Heterogeneous Palladium Catalyst for the Suzuki-Miyaura and Ullmann Coupling Reactions of Aryl Chlorides in Aqueous Media Yuan, Bizhen; Pan, Yingyi; Li, Yingwei Angewandte Chemie International Edition, Vol. 49, Issue 24 https://doi.org/10.1002/anie.201000576	journal	April 2010
Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal-Organic Frameworks Vermoortele, Frederik; Vandichel, Matthias; Van de Voorde, Ben Angewandte Chemie International Edition, Vol. 51, Issue 20 https://doi.org/10.1002/anie.201108565	journal	April 2012
Magnesium Nanocrystals Embedded in a Metal-Organic Framework: Hybrid Hydrogen Storage with Synergistic Effect on Physi- and Chemisorption Lim, Dae-Woon; Yoon, Ji Woong; Ryu, Keun Yong Angewandte Chemie International Edition, Vol. 51, Issue 39 https://doi.org/10.1002/anie.201206055	journal	September 2012
Heterogeneous Pd/C-Catalyzed Ligand-Free, Room-Temperature Suzuki–Miyaura Coupling Reactions in Aqueous Media Maegawa, Tomohiro; Kitamura, Yoshiaki; Sako, Satoko Chemistry - A European Journal, Vol. 13, Issue 20 https://doi.org/10.1002/chem.200601795	journal	July 2007
Sustainable Catalysis: Rational Pd Loading on MIL-101Cr-NH ₂ for More Efficient and Recyclable Suzuki-Miyaura Reactions Pascanu, Vlad; Yao, Qingxia; Bermejo Gómez, Antonio Chemistry - A European Journal, Vol. 19, Issue 51 https://doi.org/10.1002/chem.201302621	journal	November 2013
Influence of the Base on Pd@MIL-101-NH ₂ (Cr) as Catalyst for the Suzuki-Miyaura Cross-Coupling Reaction Carson , Fabian; Pascanu , Vlad; Bermejo Gómez , Antonio Chemistry - A European Journal, Vol. 21, Issue 30 https://doi.org/10.1002/chem.201500843	journal	June 2015
Recent Applications of the Suzuki—Miyaura Cross-Coupling Reaction in Organic Synthesis Kotha, Sambasivarao; Lahiri, Kakali; Kashinath, Dhurke ChemInform, Vol. 34, Issue 9 https://doi.org/10.1002/chin.200309228	journal	March 2003
Heterogeneous Suzuki Reactions Catalyzed by Pd(0)—Y Zeolite. Artok, Levent; Bulut, Hatice ChemInform, Vol. 35, Issue 35 https://doi.org/10.1002/chin.200435079	journal	August 2004
Highly Functionalized Biaryls via Suzuki-Miyaura Cross-Coupling Catalyzed by Pd@MOF under Batch and Continuous Flow Regimes Pascanu, Vlad; Hansen, Peter R.; Bermejo Gómez, Antonio ChemSusChem, Vol. 8, Issue 1 https://doi.org/10.1002/cssc.201402858	journal	November 2014
Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis Kotha, Sambasivarao; Lahiri, Kakali; Kashinath, Dhurke Tetrahedron, Vol. 58, Issue 48 https://doi.org/10.1016/S0040-4020(02)01188-2	journal	November 2002
Immobilization of Pd(II) on MOFs as a highly active heterogeneous catalyst for Suzuki–Miyaura and Ullmann-type coupling reactions Chen, Liyu; Gao, Zhiqiang; Li, Yingwei Catalysis Today, Vol. 245 https://doi.org/10.1016/j.cattod.2014.03.074	journal	May 2015
Utilizing mixed-linker zirconium based metal-organic frameworks to enhance the visible light photocatalytic oxidation of alcohol Goh, Tian Wei; Xiao, Chaoxian; Maligal-Ganesh, Raghu V. Chemical Engineering Science, Vol. 124 https://doi.org/10.1016/j.ces.2014.08.052	journal	March 2015
Heterogeneous Suzuki reactions catalyzed by Pd(0)–Y zeolite Artok, Levent; Bulut, Hatice Tetrahedron Letters, Vol. 45, Issue 20 https://doi.org/10.1016/j.tetlet.2004.03.126	journal	May 2004
Controlling Catalytic Properties of Pd Nanoclusters through Their Chemical Environment at the Atomic Level Using Isoreticular Metal–Organic Frameworks Li, Xinle; Goh, Tian Wei; Li, Lei ACS Catalysis, Vol. 6, Issue 6 https://doi.org/10.1021/acscatal.6b00397	journal	April 2016
Impact of Linker Engineering on the Catalytic Activity of Metal–Organic Frameworks Containing Pd(II)–Bipyridine Complexes Li, Xinle; Van Zeeland, Ryan; Maligal-Ganesh, Raghu V. ACS Catalysis, Vol. 6, Issue 9 https://doi.org/10.1021/acscatal.6b01753	journal	August 2016
Mechanism of a Suzuki-Type Homocoupling Reaction Catalyzed by Palladium Nanocubes Elias, Welman C.; Signori, Aline M.; Zaramello, Laize ACS Catalysis, Vol. 7, Issue 2 https://doi.org/10.1021/acscatal.6b03490	journal	January 2017
Water Stability and Adsorption in Metal–Organic Frameworks Burtch, Nicholas C.; Jasuja, Himanshu; Walton, Krista S. Chemical Reviews, Vol. 114, Issue 20, p. 10575-10612 https://doi.org/10.1021/cr5002589	journal	September 2014
Tandem Catalysis by Palladium Nanoclusters Encapsulated in Metal–Organic Frameworks Li, Xinle; Guo, Zhiyong; Xiao, Chaoxian ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs5006635	journal	September 2014
Palladium Nanoparticles as Efficient Green Homogeneous and Heterogeneous Carbon−Carbon Coupling Precatalysts: A Unifying View Astruc, Didier Inorganic Chemistry, Vol. 46, Issue 6 https://doi.org/10.1021/ic062183h	journal	March 2007
Influence of Connectivity and Porosity on Ligand-Based Luminescence in Zinc Metal−Organic Frameworks Bauer, Christina A.; Timofeeva, Tatiana V.; Settersten, Thomas B. Journal of the American Chemical Society, Vol. 129, Issue 22 https://doi.org/10.1021/ja0700395	journal	June 2007
Postsynthetic Ligand and Cation Exchange in Robust Metal–Organic Frameworks Kim, Min; Cahill, John F.; Fei, Honghan Journal of the American Chemical Society, Vol. 134, Issue 43 https://doi.org/10.1021/ja3079219	journal	October 2012
Engineering the Optical Response of the Titanium-MIL-125 Metal–Organic Framework through Ligand Functionalization Hendon, Christopher H.; Tiana, Davide; Fontecave, Marc Journal of the American Chemical Society, Vol. 135, Issue 30 https://doi.org/10.1021/ja405350u	journal	July 2013
Postsynthetic Metalation of Bipyridyl-Containing Metal–Organic Frameworks for Highly Efficient Catalytic Organic Transformations Manna, Kuntal; Zhang, Teng; Lin, Wenbin Journal of the American Chemical Society, Vol. 136, Issue 18 https://doi.org/10.1021/ja5018267	journal	April 2014
Molecular Encapsulation beyond the Aperture Size Limit through Dissociative Linker Exchange in Metal–Organic Framework Crystals Morabito, Joseph V.; Chou, Lien-Yang; Li, Zhehui Journal of the American Chemical Society, Vol. 136, Issue 36 https://doi.org/10.1021/ja5054779	journal	August 2014
Chemical Environment Control and Enhanced Catalytic Performance of Platinum Nanoparticles Embedded in Nanocrystalline Metal–Organic Frameworks Choi, Kyung Min; Na, Kyungsu; Somorjai, Gabor A. Journal of the American Chemical Society, Vol. 137, Issue 24 https://doi.org/10.1021/jacs.5b03540	journal	June 2015
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 Saha, Debraj; Sen, Rupam; Maity, Tanmoy Langmuir, Vol. 29, Issue 9 https://doi.org/10.1021/la304147j	journal	February 2013
Metal–organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations Chughtai, Adeel H.; Ahmad, Nazir; Younus, Hussein A. Chemical Society Reviews, Vol. 44, Issue 19 https://doi.org/10.1039/C4CS00395K	journal	January 2015
A molecular Pd( ii ) complex incorporated into a MOF as a highly active single-site heterogeneous catalyst for C–Cl bond activation Chen, Liyu; Rangan, Sylvie; Li, Jing Green Chemistry, Vol. 16, Issue 8 https://doi.org/10.1039/C4GC00314D	journal	January 2014
Facile preparation of Pd nanoparticles supported on single-layer graphene oxide and application for the Suzuki–Miyaura cross-coupling reaction Yamamoto, Shun-ichi; Kinoshita, Hiroshi; Hashimoto, Hideki Nanoscale, Vol. 6, Issue 12 https://doi.org/10.1039/C4NR00715H	journal	January 2014
Phosphine-stabilized Pd nanoparticles supported on silica as a highly active catalyst for the Suzuki–Miyaura cross-coupling reaction Sahu, Debojeet; Das, Pankaj RSC Advances, Vol. 5, Issue 5 https://doi.org/10.1039/C4RA11186A	journal	January 2015
Metal−organic framework encapsulated Pd nanoparticles: towards advanced heterogeneous catalysts Chen, Liyu; Chen, Huirong; Luque, Rafael Chem. Sci., Vol. 5, Issue 10 https://doi.org/10.1039/C4SC01847H	journal	January 2014
Chitosan-based heterogeneous catalysts for Suzuki and Heck reactions Hardy, Jeff J. E.; Hubert, Sandrine; Macquarrie, Duncan J. Green Chemistry, Vol. 6, Issue 1 https://doi.org/10.1039/b312145n	journal	January 2004
Mechanical properties of hybrid inorganic–organic framework materials: establishing fundamental structure–property relationships Tan, Jin Chong; Cheetham, Anthony K. Chemical Society Reviews, Vol. 40, Issue 2 https://doi.org/10.1039/c0cs00163e	journal	January 2011
Unexpected activation of carbon–bromide bond promoted by palladium nanoparticles in Suzuki C–C couplings Sanhes, Delphine; Raluy, Eva; Rétory, Stéphane Dalton Transactions, Vol. 39, Issue 40 https://doi.org/10.1039/c0dt00201a	journal	January 2010
Pd nanoparticles for C–C coupling reactions Balanta, Angelica; Godard, Cyril; Claver, Carmen Chemical Society Reviews, Vol. 40, Issue 10 https://doi.org/10.1039/c1cs15195a	journal	January 2011
Interrogating the catalytic mechanism of nanoparticle mediated Stille coupling reactions employing bio-inspired Pd nanocatalysts Pacardo, Dennis B.; Slocik, Joseph M.; Kirk, Kyle C. Nanoscale, Vol. 3, Issue 5 https://doi.org/10.1039/c1nr10089k	journal	January 2011
Catalysis by metal nanoparticles embedded on metal–organic frameworks Dhakshinamoorthy, Amarajothi; Garcia, Hermenegildo Chemical Society Reviews, Vol. 41, Issue 15 https://doi.org/10.1039/c2cs35047e	journal	January 2012
The Chemistry and Applications of Metal-Organic Frameworks Furukawa, H.; Cordova, K. E.; O'Keeffe, M. Science, Vol. 341, Issue 6149, p. 1230444-1230444 https://doi.org/10.1126/science.1230444	journal	August 2013
The Use of Palladium on Magnetic Support as Catalyst for Suzuki–Miyaura Cross-Coupling Reactions Sydnes, Magne Catalysts, Vol. 7, Issue 12 https://doi.org/10.3390/catal7010035	journal	January 2017

Cited By (1)

1,10‐Phenanthroline Carboxylic Acids for Preparation of Functionalized Metal‐Organic Frameworks Abel, Anton S.; Yu Mitrofanov, Alexander; Yakushev, Aleksei A. Asian Journal of Organic Chemistry, Vol. 8, Issue 11 https://doi.org/10.1002/ajoc.201900569	journal	September 2019

Figures / Tables (4)

Similar Records

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

Journal Article · Mon Aug 08 20:00:00 EDT 2016 · ACS Catalysis · OSTI ID:1337683

Dioxin-Linked Covalent Organic Framework-Supported Palladium Complex for Rapid Room-Temperature Suzuki–Miyaura Coupling Reaction

Journal Article · Wed Aug 16 20:00:00 EDT 2023 · Crystals · OSTI ID:2337856

Elucidating the Nanoparticle–Metal Organic Framework Interface of Pt@ZIF-8 Catalysts

Journal Article · Mon Nov 06 23:00:00 EST 2017 · Journal of Physical Chemistry. C · OSTI ID:1482385

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Heterogeneous catalysis
Isoreticular metal–organic frameworks
Structure–activity relationship
Suzuki–Miyaura cross-coupling

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]

Citation Formats

References (43)

Cited By (1)

Figures / Tables (4)

Similar Records

Related Subjects