A new heterogeneous catalyst for epoxidation of alkenes via one-step post-functionalization of IRMOF-3 with a manganese(ii) acetylacetonate complex

Bhattacharjee, Samiran; Yang, Da-Ae; Ahn, Wha‐Seung

doi:10.1039/c1cc00069a

Cited by 134 publications

(65 citation statements)

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“…Instead of using TBHP as an oxidant they utilized O 2 in combination with trimethylacetaldehyde as a co-oxidant. Good conversions (even for the more bulky cyclooctene) were obtained with very high selectivities toward the epoxide (>80%) 105 .…”

Section: Pom@mofmentioning

confidence: 93%

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Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

2014

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Since the discovery of Metal Organic Frameworks (MOFs) in the early 1990, the amount of new structures has grown exponentially. A MOF typically consists of inorganic nodes that are connected by organic linkers to form crystalline, highly porous structures. MOFs have attracted a lot of attention lately, as the versatile design of such materials holds promises of interesting applications in various fields. In this review, we will focus on the use of MOFs as heterogeneous oxidation catalysts. MOFs are very promising candidates to replace homogeneous catalysts by sustainable and stable heterogeneous catalysts. The catalytic active function can be either the active metal sites of the MOF itself or can be introduced as an extra functionality in the linker, a dopant or a "ship-in-a-bottle" complex. As the pore size, pore shape and functionality of MOFs can be designed in numerous ways, shape selectivity and even chiral selectivity can be created. In this review, we will present an overview on the state of the art of the use of MOFs as a heterogeneous catalyst in liquid phase oxidation reactions.

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Section: Pom@mofmentioning

confidence: 93%

“…However, the VO(acac) 2 @IRMOF-3 showed a rather low catalytic activity and stability 104 . The group of Ahn reported a more straightforward one step functionalization of the IRMOF-3 with a manganese complex (entry 21 Table 4) 105 . Instead of using TBHP as an oxidant they utilized O 2 in combination with trimethylacetaldehyde as a co-oxidant.…”

Section: Pom@mofmentioning

confidence: 99%

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

2014

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“…via the one-step post-synthetic functionalization of IRMOF-3 [56] hydrochloride in methanol in the presence of sodium hydroxide at 333 K to produce an imine derivative, which was reacted further with manganese (II) acetate to form a Mn(II)-immobilized hybrid material, ZIF-90-S[Mn] (Scheme 4). FTIR, BET surface area measurements, thermogravimetric analysis, and chemical analysis confirmed the successful post-synthesis modification and metalation.…”

Section: Direct and Post-synthesis Organic Functionalizationmentioning

confidence: 99%

“…The BET surface area of the sample was 2190 m 2 /g, which was significantly higher than previously reported for bifunctional MIL-101-NH 2 -SO 3 H prepared using a three-step process (638 m 2 /g) [55]. A novel route to bind the active homogeneous catalytic species, Mn(II) acetylacetonate, to IRMOF-3 was conducted via Schiff base condensation between the free amino group of IRMOF-3 and the carbonyl groups of the manganese(II) complex to form a new hybrid material, IRMOF-3[Mn] (Scheme 3) [56]. XRD, N 2 adsorptiondesorption isotherms, thermogravimetric analysis, Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy, 1 H nuclear magnetic resonance (NMR) spectroscopy, and elemental analysis confirmed the functional group and post-synthesis metalation in IRMOF-3 [Mn].…”

Section: Direct and Post-synthesis Organic Functionalizationmentioning

confidence: 99%

Metal–Organic Frameworks for Catalysis

et al. 2015

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Metal-organic frameworks (MOFs) are a relatively new class of porous material, which are comprised of metal ions or clusters linked with poly-functional organic molecules. MOFs have been studied increasingly for heterogeneous catalysis applications because these hybrid materials have well-ordered tunable porous structures with exceptional textural properties and introduction of additional active sites can be carried out easily by relatively simple post-synthesis functionalization. This short review focuses on recent works on liquid phase catalytic reactions carried out over selected MOFs. The MOF membranes for catalysis and the potential of functionalized MOF materials for chiral reactions are also mentioned briefly.

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“…These materials have been investigated actively for potential energy storage, CO 2 capture, hydrocarbon adsorption/separation, and catalysis owing to their high surface areas in uniformly sized pores as well as the high metal content in high dispersion. [11][12][13][14] Song et al examined the cycloaddition of CO 2 to propylene epoxide over MOF-5 with a quaternary ammonium salt as a co-catalyst, 15 whereas ZIF-8 and Cu 3 (BTC) 2 were tested for the cycloaddition of epichlorohydrin (ECH) without employing a solvent. 16,17 Mg-MOF-74 was effective not only for CO 2 capture but also for its chemical conversion via a cycloaddition reaction.…”

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confidence: 99%

CO₂ Cycloaddition of Epichlorohydrin over NH₂‐Functionalized MIL‐101

Jang

Lee

Ahn

2015

Bulletin Korean Chem Soc

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CO 2 is the major greenhouse gas suspected to cause global warming, and various CO 2 capture and sequestration technologies using liquid amines or solid-phase sorbents to remedy the situation have been evaluated. [1][2][3] Chemical conversion of CO 2 is also being considered as a means of sequestration, because CO 2 can be an attractive C 1 building block that can be converted to valuable chemical products. In this regard, the cycloaddition reaction is one of the most promising reactions for CO 2 currently under consideration. In this process, cyclic carbonates are produced by the coupling of carbon dioxide with various epoxides. [4][5][6] These carbonates are used widely in industry as solvents, monomers, and pharmaceutical and fine-chemical intermediates. 7 A range of homogeneous catalysts, such as ionic liquids, or transition-metal complexes, such as Re(CO) 5 Br or Co(III)-salen, [8][9][10] have been used to produce cyclic carbonates. On the other hand, the frequent necessity to employ a base promoter and the rigorous purification process required for catalyst separation are significant limitations. A heterogeneous catalyst that can promote the reaction under mild reaction conditions would be highly desirable.Metal-organic frameworks (MOFs) are crystalline organicinorganic hybrid structures formed by the coordination of metal ions or clusters with multidentate organic linkers. These materials have been investigated actively for potential energy storage, CO 2 capture, hydrocarbon adsorption/separation, and catalysis owing to their high surface areas in uniformly sized pores as well as the high metal content in high dispersion. 11-14Song et al. examined the cycloaddition of CO 2 to propylene epoxide over MOF-5 with a quaternary ammonium salt as a co-catalyst, 15 whereas ZIF-8 and Cu 3 (BTC) 2 were tested for the cycloaddition of epichlorohydrin (ECH) without employing a solvent. 16,17 Mg-MOF-74 was effective not only for CO 2 capture but also for its chemical conversion via a cycloaddition reaction.18 Recently, amine-functionalized was reported to be promising for the cycloaddition of styrene oxide with CO 2 , and the catalytic activity was correlated with the concerted contribution by Lewis acid/base sites on the MOF catalysts. MIL-101 is a chromium-benzenedicarboxylate MOF having a high surface area with excellent stability against moisture and other chemicals, and has been applied to a wide range of chemical reactions either as a catalyst or as support material. [20][21][22] In this study, the amine-functionalized MIL-101 structures were prepared by two different routes: direct solvothermal method using 2-aminobenzene-1,4-dicarboxylate as a ligand, and post-synthesis grafting of diethylenetriamine (DETA) onto the Cr open metal sites. The materials were studied as a catalyst for the cycloaddition of CO 2 to ECH. The amine-functionalized MIL-101 structures were found to be active catalysts for the catalytic cycloaddition of CO 2 to a range of epoxides in an organic solvent, and control of the relative amounts ...

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A new heterogeneous catalyst for epoxidation of alkenes via one-step post-functionalization of IRMOF-3 with a manganese(ii) acetylacetonate complex

Abstract: A manganese(II) acetylacetonate complex has been immobilized to the metal-organic framework IRMOF-3 through a one-step post-synthetic route for the first time, providing an effective and recyclable heterogeneous catalyst for epoxidation of alkenes.

Cited by 134 publications

References 32 publications

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

Metal–Organic Frameworks for Catalysis

CO₂ Cycloaddition of Epichlorohydrin over NH₂‐Functionalized MIL‐101

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A new heterogeneous catalyst for epoxidation of alkenes via one-step post-functionalization of IRMOF-3 with a manganese(ii) acetylacetonate complex

Abstract: A manganese(II) acetylacetonate complex has been immobilized to the metal-organic framework IRMOF-3 through a one-step post-synthetic route for the first time, providing an effective and recyclable heterogeneous catalyst for epoxidation of alkenes.

Cited by 134 publications

References 32 publications

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

Metal–Organic Frameworks for Catalysis

CO2 Cycloaddition of Epichlorohydrin over NH2‐Functionalized MIL‐101

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CO₂ Cycloaddition of Epichlorohydrin over NH₂‐Functionalized MIL‐101