Chloromethylation as a functionalisation pathway for metal–organic frameworks

Goesten, Maarten G.; Gupta, Karthick Babu Sai Sankar; Ramos‐Fernández, Enrique V.; Khajavi, Hossein; Gascón, Jorge; Kapteijn, Freek

doi:10.1039/c2ce06594k

Cited by 48 publications

(48 citation statements)

References 31 publications

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“…These materials are very popular thanks to their potential in gas adsorption technologies, 1 biomedical applications, 2,3 and catalysis. [8][9][10][11][12] Incorporation of phosphine functional groups inside structures with new and existing topologies is achieved using direct solvothermal synthesis, postsynthetic modification 13 or the co-crystallization of organic linkers with similar connectivity, 14 We and other groups foresee new applications for such materials in transition metal immobilization and catalysis. 7 Organophosphine moieties were recently introduced to yield crystalline phosphine MOFs (P-MOFs).…”

Section: Introductionmentioning

confidence: 99%

Phosphine and phosphine oxide groups in metal–organic frameworks detected by P K-edge XAS

Morel

Huthwelker

et al. 2015

Phys. Chem. Chem. Phys.

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Phosphine metal-organic frameworks (P-MOFs) are crystalline porous coordination polymers that contain phosphorus functional groups within their pores. We present the use of X-ray absorption spectroscopy (XAS) at the P K-edge to determine the phosphine to phosphine oxide ratio in two P-MOFs with MIL-101 topology. The phosphorus oxidation state is of particular interest as it strongly influences the coordination affinity of these materials for transition metals. This method can determine the oxidation state of phosphorus even when the material contains paramagnetic nuclei, differently from NMR spectroscopy. We observed that phosphine in LSK-15 accounts for 72 ± 4% of the total phosphorus groups and that LSK-12 contains only phosphine oxide.

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Section: Introductionmentioning

confidence: 99%

Phosphine and phosphine oxide groups in metal–organic frameworks detected by P K-edge XAS

Morel

Huthwelker

et al. 2015

Phys. Chem. Chem. Phys.

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“…The Pd−NHC−MIL‐101(Cr) catalyst was prepared using a three‐step synthetic pathway (Scheme ). First, the MIL‐101(Cr) was reacted with 2‐methoxyacetyl chloride in the presence of AlCl 3 as a known reagent for the chloromethylation of the benzene ring in the structure of MOF . Then, the chloromethylated MOF was reacted with 1‐methyl‐ 1H ‐imidazole in order to form imidazolium moieties in the structure of MOF .…”

Section: Resultsmentioning

confidence: 99%

Immobilized Pd on a NHC functionalized metal–organic framework MIL‐101(Cr): an efficient heterogeneous catalyst in Suzuki−Miyaura coupling reaction in water

Niknam

Panahi

Khalafi‐Nezhad

2020

Applied Organom Chemis

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A novel Pd−NHC functionalized metal–organic framework (MOF) based on MIL‐101(Cr) was synthesized and used as an efficient heterogeneous catalyst in the C‐C bond formation reactions. Using this heterogeneous Pd catalyst system, the Suzuki−Miyaura coupling reaction was accomplished well in water, and coupling products were obtained in good to excellent yields in short reaction time. The Pd−NHC−MIL‐101(Cr) was characterized using some different techniques, including Fourier transform‐infrared, X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy, inductively coupled plasma and elemental analysis. The microscopic techniques showed the discrete octahedron structure of MIL‐101(Cr), which is also stable after chemical modification process to prepare the catalyst system. The TEM images of the catalyst showed the existence of palladium nanoparticles immobilized in the structure of the catalyst, while no reducing agent was used. It seems that the NHC groups and imidazolium moieties in the structure of the MOF can reduce Pd (II) to Pd (0) species. This modified MOF substrate can also prevent aggregation of Pd nanoparticles, resulting in high stability of them in organic transformation. The Pd−NHC−MIL‐101(Cr) catalyst system could be simply extracted from the reaction mixture, providing an efficient synthetic method for the synthesis of biaryls derivatives using the aforementioned coupling reaction. The Pd−NHC−MIL‐101(Cr) catalyst could be recycled in this organic reaction with almost consistent catalytic efficiency.

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“…However its use as a carrier material for catalytically active sites is severely limited by the lack of any functional groups available for postmodification. The chloromethylation procedure proposed by Goesten et al [47] is an excellent way to solve this. The procedure is relatively mild, and is applicable to structures which are far less stable than the proposed material.…”

Section: Selectivity Of Asymmetric Grafted Complexesmentioning

confidence: 99%

“…In order to introduce an anchor point for further postmodification a chloromethylation reaction as proposed earlier by Goesten et al [47] was used. 1 g of MIL-101 (±1.3 mmol) was suspended in 70 ml of nitromethane together with 7.8 mmol of AlCl 3 .6H 2 O and 3.6 mmol of methoxyacetyl chloride.…”

Section: Chloromethylationmentioning

confidence: 99%

The enantioselectivity of the manganese-salen complex in the epoxidation of unfunctionalized olefins and the influence of grafting

Bogaerts

Wouters

Voort

et al. 2015

Journal of Molecular Catalysis A: Chemical

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Chloromethylation as a functionalisation pathway for metal–organic frameworks

Cited by 48 publications

References 31 publications

Phosphine and phosphine oxide groups in metal–organic frameworks detected by P K-edge XAS

Phosphine and phosphine oxide groups in metal–organic frameworks detected by P K-edge XAS

Immobilized Pd on a NHC functionalized metal–organic framework MIL‐101(Cr): an efficient heterogeneous catalyst in Suzuki−Miyaura coupling reaction in water

The enantioselectivity of the manganese-salen complex in the epoxidation of unfunctionalized olefins and the influence of grafting

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