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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]

Journal Article · · Catalysis Letters

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.

Research Organization:
Ames Lab., 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, Vol. 148, Issue 3; ISSN 1011-372X
Publisher:
SpringerCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

References (43)

Metal–organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations journal January 2015
Catalysis by metal nanoparticles embedded on metal–organic frameworks journal January 2012
Chemical Environment Control and Enhanced Catalytic Performance of Platinum Nanoparticles Embedded in Nanocrystalline Metal–Organic Frameworks journal June 2015
Postsynthetic Metalation of Bipyridyl-Containing Metal–Organic Frameworks for Highly Efficient Catalytic Organic Transformations journal April 2014
Postsynthetic Ligand and Cation Exchange in Robust Metal–Organic Frameworks journal October 2012
Facile preparation of Pd nanoparticles supported on single-layer graphene oxide and application for the Suzuki–Miyaura cross-coupling reaction journal January 2014
Sustainable Catalysis: Rational Pd Loading on MIL-101Cr-NH 2 for More Efficient and Recyclable Suzuki-Miyaura Reactions journal November 2013
Molecular Encapsulation beyond the Aperture Size Limit through Dissociative Linker Exchange in Metal–Organic Framework Crystals journal August 2014
Heterogeneous Suzuki reactions catalyzed by Pd(0)–Y zeolite journal May 2004
The Use of Palladium on Magnetic Support as Catalyst for Suzuki–Miyaura Cross-Coupling Reactions journal January 2017
Interrogating the catalytic mechanism of nanoparticle mediated Stille coupling reactions employing bio-inspired Pd nanocatalysts journal January 2011
Phosphine-stabilized Pd nanoparticles supported on silica as a highly active catalyst for the Suzuki–Miyaura cross-coupling reaction journal January 2015
Controlling Catalytic Properties of Pd Nanoclusters through Their Chemical Environment at the Atomic Level Using Isoreticular Metal–Organic Frameworks journal April 2016
Immobilization of Pd(II) on MOFs as a highly active heterogeneous catalyst for Suzuki–Miyaura and Ullmann-type coupling reactions journal May 2015
Mechanical properties of hybrid inorganic–organic framework materials: establishing fundamental structure–property relationships journal January 2011
Chitosan-based heterogeneous catalysts for Suzuki and Heck reactions journal January 2004
Water Stability and Adsorption in Metal–Organic Frameworks journal September 2014
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
Magnesium Nanocrystals Embedded in a Metal-Organic Framework: Hybrid Hydrogen Storage with Synergistic Effect on Physi- and Chemisorption journal September 2012
Utilizing mixed-linker zirconium based metal-organic frameworks to enhance the visible light photocatalytic oxidation of alcohol journal March 2015
Highly Functionalized Biaryls via Suzuki-Miyaura Cross-Coupling Catalyzed by Pd@MOF under Batch and Continuous Flow Regimes journal November 2014
A Highly Active Heterogeneous Palladium Catalyst for the Suzuki-Miyaura and Ullmann Coupling Reactions of Aryl Chlorides in Aqueous Media journal April 2010
Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis journal November 2002
Engineering the Optical Response of the Titanium-MIL-125 Metal–Organic Framework through Ligand Functionalization journal July 2013
Unexpected activation of carbon–bromide bond promoted by palladium nanoparticles in Suzuki C–C couplings journal January 2010
Heterogeneous Pd/C-Catalyzed Ligand-Free, Room-Temperature Suzuki–Miyaura Coupling Reactions in Aqueous Media journal July 2007
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
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
Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal-Organic Frameworks journal April 2012
Influence of Connectivity and Porosity on Ligand-Based Luminescence in Zinc Metal−Organic Frameworks journal June 2007
Influence of the Base on Pd@MIL-101-NH 2 (Cr) as Catalyst for the Suzuki-Miyaura Cross-Coupling Reaction journal June 2015
Palladium Nanoparticles as Efficient Green Homogeneous and Heterogeneous Carbon−Carbon Coupling Precatalysts:  A Unifying View journal March 2007
Impact of Linker Engineering on the Catalytic Activity of Metal–Organic Frameworks Containing Pd(II)–Bipyridine Complexes journal August 2016
The Chemistry and Applications of Metal-Organic Frameworks journal August 2013
Metal−organic framework encapsulated Pd nanoparticles: towards advanced heterogeneous catalysts journal January 2014
Tandem Catalysis by Palladium Nanoclusters Encapsulated in Metal–Organic Frameworks journal September 2014
Pd nanoparticles for C–C coupling reactions journal January 2011
Mechanism of a Suzuki-Type Homocoupling Reaction Catalyzed by Palladium Nanocubes journal January 2017
A Highly Active Heterogeneous Palladium Catalyst for the Suzuki-Miyaura and Ullmann Coupling Reactions of Aryl Chlorides in Aqueous Media journal April 2010
Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal-Organic Frameworks journal April 2012
Recent Applications of the Suzuki—Miyaura Cross-Coupling Reaction in Organic Synthesis journal March 2003
Heterogeneous Suzuki Reactions Catalyzed by Pd(0)—Y Zeolite. journal August 2004
Magnesium Nanocrystals Embedded in a Metal-Organic Framework: Hybrid Hydrogen Storage with Synergistic Effect on Physi- and Chemisorption journal September 2012

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