Expanding applications of copper-based metal–organic frameworks in catalysis: Oxidative C–O coupling by direct C–H activation of ethers over Cu2(BPDC)2(BPY) as an efficient heterogeneous catalyst

• Published in: Journal of catalysis Vol. 306; pp. 38 - 46
• Main Authors: Phan, Nam T.S., Vu, Phuong H.L., Nguyen, Tung T.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier Inc 01.10.2013; Elsevier; Elsevier BV
• Subjects: atomic absorption spectrometry; Catalysis; Catalysts; catalytic activity; Catalytic oxidation; Chemistry; coordination polymers; Copper; Cross-dehydrogenative; Cu2(BPDC)2(BPY); C–H activation; ethers; Exact sciences and technology; Fourier transform infrared spectroscopy; General and physical chemistry; Heterogeneous catalyst; hydrogen; Metal–organic framework; nitrogen; phenols; scanning electron microscopy; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; thermogravimetry; transmission electron microscopy; X-ray diffraction; Metal–organic framework; Heterogeneous catalyst; C–H activation; Cross-dehydrogenative; Cu2(BPDC)2(BPY); Metal organic framework; Catalytic reaction; Ether; Transition metal; Activation; BPY; Oxidative coupling; Heterogeneous catalysis; Cu; BPDC; C-H activation; Metal―organic framework; Copper
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2013.06.006

The metal-organic framework Cu2(BPDC)2(BPY) exhibited high catalytic activity in the copper-catalyzed cross-dehydrogenative coupling reaction of ethers with 2-carbonyl-substituted phenols. [Display omitted] •Cu2(BPDC)2(BPY) was used as catalyst for the reaction of ethers with phenols.•The catalyst exhibited significantly higher activity than that of other Cu-MOFs.•The catalyst could be recovered and reused. A crystalline porous metal–organic framework Cu2(BPDC)2(BPY) was synthesized and characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) spectra, atomic absorption spectrophotometry (AAS), hydrogen temperature-programmed reduction (H2-TPR), and nitrogen physisorption measurements. The Cu-MOF could be used as an efficient heterogeneous catalyst for the copper-catalyzed cross-dehydrogenative coupling reaction of ethers with 2-carbonyl-substituted phenols. The Cu2(BPDC)2(BPY) exhibited significantly higher catalytic activity than that of other Cu-MOFs such as Cu3(BTC)2, Cu(BDC), and Cu(BPDC). The Cu-MOF also offered advantages over several copper salts such as CuCl2, CuCl, CuI, Cu(NO3)2, and Cu(OAc)2 in terms of the catalytic activity as well as the catalyst reusability. To the best of our knowledge, the cross-dehydrogenative coupling reaction of ethers with 2-carbonyl-substituted phenols via C–H activation under oxidative conditions using a heterogeneous catalyst was not previously mentioned in the literature.