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Immobilization of Pd(II) on MOFs as a highly active heterogeneous catalyst for Suzuki–Miyaura and Ullmann-type coupling reactions

Paper ID Volume ID Publish Year Pages File Format Full-Text
54049 46994 2015 7 PDF Available
Title
Immobilization of Pd(II) on MOFs as a highly active heterogeneous catalyst for Suzuki–Miyaura and Ullmann-type coupling reactions
Abstract

•Pd(II) was immobilized on MOF-253 through post-synthetic modification.•MOF-253·PdCl2 showed higher activity than its homogeneous counterparts.•The material was highly active in coupling reactions of a variety of aryl halides.•The catalyst could be reused up to five times without any loss in activity.

Palladium chloride was successfully immobilized on MOF-253, a MOF material with un-coordinated 2,2′-bipyridine moieties, through post-synthetic modification. The coordination interaction between the 2,2′-bipyridine moieties and Pd cations in the MOF-253·PdCl2 material was demonstrated by X-ray photoelectron spectroscopy (XPS) analysis. The prepared MOF-253·0.05PdCl2 was shown to be highly active, selective, and recyclable for the Suzuki–Miyaura cross-coupling and Ullmann homocoupling of a wide range of aryl halides including electron-rich and electron-poor aryl iodides/bromides, heteroaryl iodides, and even aryl chlorides, affording the corresponding biaryl compounds in good to excellent yields under mild reaction conditions. It is suggested that the 2,2′-bipyridine moieties in MOF-253 provide electron-rich environment for Pd(II) cations, and thus facilitate the initial adsorption and insertion of aryl halides molecules to Pd active sites during the carbon–carbon coupling reactions. Moreover, MOF-253·PdCl2 showed remarkably higher activity than the homogeneous Pd(bpy)Cl2 and PdCl2(CH3CN)2, which might be due to the presence of charge transfers between adjacent ligands and metals in the MOF catalyst. The superior catalytic performances of metal ions immobilized on MOFs to their homogenous counterparts might bring new opportunities in the development of highly efficient metal catalysts combining advantages of both homogeneous and heterogeneous catalysis.

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Keywords
Aryl halide; CC coupling; Heterogeneous catalysis; Metal-organic frameworks; Palladium
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Immobilization of Pd(II) on MOFs as a highly active heterogeneous catalyst for Suzuki–Miyaura and Ullmann-type coupling reactions
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Publisher
Database: Elsevier - ScienceDirect
Journal: Catalysis Today - Volume 245, 1 May 2015, Pages 122–128
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Catalysis
Get Full-Text Now
Don't Miss Today's Special Offer
Price was $35.95
You save - $31
Price after discount Only $4.95
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Full-text PDF Download
Online Support
Any Questions? feel free to contact us