{[Co 2 (btec)(2,2′-bipy) 2 ]·H 2 O} n metal–organic framework: Structure and activity in the solvent-free oxidation of cyclohexene with oxygen

Hao, Jianmin; Li, Sijia; Han, Limin; Cheng, Lin; Suo, Quan‐Ling; Xiao, Yang; Jiao, Xiaoli; Feng, Xuemin; Bai, Weiwei; Song, Xiaofei

doi:10.1016/j.ica.2014.06.005

Cited by 12 publications

(7 citation statements)

References 31 publications

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“…Epoxidation of alkenes is one of the well-known reactions in the industry for synthesis organic products which is catalyzed by many metal salts under both homogeneous and heterogeneous catalysts. − Herein, the heterogeneous catalytic activity of MOFs was carried out using tert -butyl hydroperoxide ( t -BuOOH) as an oxidant in acetonitrile media at 70 °C for 20 h. Owing to the high thermal stabilities of compounds 1 , 2 , and 3a , they were used as catalysts for the alkenes epoxidation. To find the suitable conditions for epoxidation, the effects of solvent, oxidant, and temperature of the reaction were examined by using trans -stilbene as a model substrate.…”

Section: Resultsmentioning

confidence: 99%

Thermally Induced Single-Crystal-to-Single-Crystal Transformation and Heterogeneous Catalysts for Epoxidation Reaction of Co(II) Based Metal–Organic Frameworks Containing 1,4-Phenylenediacetic Acid

Othong

Boonmak

et al. 2017

Crystal Growth & Design

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Four new metal−organic frameworks (MOFs) based on 1,4-phenylenediacetic acid (1,4-H 2 phda), [Co(1,4-phda)(4,4′-bpa)] (1), [Co(1,4-phda)(4,4′-bpp)] (2), [Co(1,4-phda)(4,4′-bpa)(H 2 O) 2 ] (3), and [Co(1,4-phda)-(4,4′-bpa)] (3a) (4,4′-bpa = 1,2-bis(4-pyridyl)ethane and 4,4′-bpp = 1,3-bis(4-pyridyl)propane) were successfully synthesized. The various synthetic methods play an important role in the formation of diverse structural frameworks.Compound 1 shows a 3D framework, while 2, 3, and 3a exhibit 2D layered MOFs with different architectures. The irreversible thermally induced single-crystal-to-single-crystal transformation with chromotropism from 3 to 3a was observed, which was established by the breakage and reformation of coordination bonds around Co(II) centers. The orientation of coordinated 4,4′-bpa ligand and conformation of 1,4-phda ligand play a key role on pore opening in 3 and pore closing in 3a. Furthermore, the functional properties as heterogeneous catalysts of these MOFs including epoxidation of alkenes and photocatalytic performance for MB degradation have been investigated. The heterogeneous catalytic properties of 1, 2, and 3a exhibit high catalytic activity with good catalyst stability.

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Section: Resultsmentioning

confidence: 99%

Thermally Induced Single-Crystal-to-Single-Crystal Transformation and Heterogeneous Catalysts for Epoxidation Reaction of Co(II) Based Metal–Organic Frameworks Containing 1,4-Phenylenediacetic Acid

Othong

Boonmak

et al. 2017

Crystal Growth & Design

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“…On the other hand, a more direct comparison is possible with the 1D CP reported by Hao et al 75 In this work, polymer [Co(dpa)(2,2′-bipy)(H 2 O) 2 ] n (dpa= 2,2′-diphenic acid) (4) is used as a catalyst and the process is carried out using oxygen as an oxidant, with no co-oxidant. This system presents a slightly distorted octahedral geometry with two water molecules in the first coordination sphere.…”

Section: ■ Introductionmentioning

confidence: 92%

Phenylalanine-Based Co²⁺ and Cd²⁺ 1D Coordination Polymers: Structural Properties and Catalytic Application for Solvent-Free Aerobic Oxidation of Cycloalkene

Movilla,

Rey,

Saleta

et al. 2023

Inorg. Chem.

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Two 1D coordination polymers (CPs) with general formula [M(L)(H 2 O)(AcO)] n , (M = Co (1) or Cd (2), AcO = acetate anion and L denotes L-phenylalanine based ligand), were synthesized and fully characterized by various spectroscopies (UV− vis, FTIR, and NMR), thermal techniques, magnetic measurements (for 1), and single-crystal and powder X-ray diffraction studies. They can be described as "ribbon-like" 1D polymers constructed through a zigzag arrangement. The polymeric structure is developed due to the coordination mode adopted by the amino acid ligand, classified as μ 3 -N 1 O 1 :O 1 :O 2 , which simultaneously links three metal centers. This moiety also plays an important role as a magnetic coupler between metal centers in the cobalt system, which shows a weak antiferromagnetic interaction. Both CPs have also been used in the catalytic oxidation of cyclohexene with molecular oxygen (O 2 ) as an oxidant. Under mild conditions, both compounds demonstrated remarkable catalytic activity, with the cobalt system being more efficient than the cadmium analogue (conversion: 73 and 58% and selectivity for the major product, 2-cyclohexanone: 63 and 55%, for 1 and 2, respectively). Leaching experiments and the results obtained using a radical quencher are consistent with a radical-mediated mechanism for the Co compound. The presence of the superoxide radical was also confirmed using EPR spectroscopy and DMPO as a spin trap, which was further validated by DFT calculations. The activity observed for the Cd analogue is attributed to the organic scaffold assisted by the templating effect of the metal ion.

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“…Co(II)-based MOF, {[Co 2 (-btec)(2,2 -bipy) 2 ]H 2 O}n (btec: 1,2,4,5-benzenetetracarboxylic acid; 2,2 -bipy: 2,2 -bipyridine) was prepared and its catalytic activity was studied in the aerobic oxidation of cyclohexene under solvent-free conditions [50]. The structural X-ray analysis of {[Co 2 (-btec)(2,2 -bipy) 2 ]H 2 O} n revealed that it crystallizes in the orthorhombic space group C 222 1.…”

Section: Olefin Oxidationmentioning

confidence: 99%

Cobalt-Based Metal Organic Frameworks as Solids Catalysts for Oxidation Reactions

et al. 2021

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Metal organic frameworks (MOFs) are porous crystalline solids whose frameworks are constituted by metal ions/nodes with rigid organic linkers leading to the formation of materials having high surface area and pore volume. One of the unique features of MOFs is the presence of coordinatively unsaturated metal sites in their crystalline lattice that can act as Lewis acid sites promoting organic transformations, including aerobic oxidation reactions of various substrates such as hydrocarbons, alcohols, and sulfides. This review article summarizes the existing Co-based MOFs for oxidation reactions organized according to the nature of substrates like hydrocarbon, alcohol, olefin, and water. Both aerobic conditions and peroxide oxidants are discussed. Emphasis is placed on comparing the advantages of using MOFs as solid catalysts with respect to homogeneous salts in terms of product selectivity and long-term stability. The final section provides our view on future developments in this field.

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{[Co 2 (btec)(2,2′-bipy) 2 ]·H 2 O} n metal–organic framework: Structure and activity in the solvent-free oxidation of cyclohexene with oxygen

Cited by 12 publications

References 31 publications

Thermally Induced Single-Crystal-to-Single-Crystal Transformation and Heterogeneous Catalysts for Epoxidation Reaction of Co(II) Based Metal–Organic Frameworks Containing 1,4-Phenylenediacetic Acid

Thermally Induced Single-Crystal-to-Single-Crystal Transformation and Heterogeneous Catalysts for Epoxidation Reaction of Co(II) Based Metal–Organic Frameworks Containing 1,4-Phenylenediacetic Acid

Phenylalanine-Based Co²⁺ and Cd²⁺ 1D Coordination Polymers: Structural Properties and Catalytic Application for Solvent-Free Aerobic Oxidation of Cycloalkene

Cobalt-Based Metal Organic Frameworks as Solids Catalysts for Oxidation Reactions

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{[Co 2 (btec)(2,2′-bipy) 2 ]·H 2 O} n metal–organic framework: Structure and activity in the solvent-free oxidation of cyclohexene with oxygen

Cited by 12 publications

References 31 publications

Thermally Induced Single-Crystal-to-Single-Crystal Transformation and Heterogeneous Catalysts for Epoxidation Reaction of Co(II) Based Metal–Organic Frameworks Containing 1,4-Phenylenediacetic Acid

Thermally Induced Single-Crystal-to-Single-Crystal Transformation and Heterogeneous Catalysts for Epoxidation Reaction of Co(II) Based Metal–Organic Frameworks Containing 1,4-Phenylenediacetic Acid

Phenylalanine-Based Co2+ and Cd2+ 1D Coordination Polymers: Structural Properties and Catalytic Application for Solvent-Free Aerobic Oxidation of Cycloalkene

Cobalt-Based Metal Organic Frameworks as Solids Catalysts for Oxidation Reactions

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Phenylalanine-Based Co²⁺ and Cd²⁺ 1D Coordination Polymers: Structural Properties and Catalytic Application for Solvent-Free Aerobic Oxidation of Cycloalkene