Catalytic applications of CuII-containing MOFs based on N-heterocyclic ligand in the oxidative coupling of 2,6-dimethylphenol

Xiao, Bo; Hou, Hongwei; Fan, Yaoting

doi:10.1016/j.jorganchem.2007.01.010

Cited by 70 publications

(23 citation statements)

References 47 publications

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“…The CÀO/CÀC oxidative coupling selectivities are comparable to those obtained for other homo-and heterogeneous catalysts (up to 90 % CÀO/CÀC coupling under optimised reaction conditions), and display good substrate-tocatalyst ratios as well as short reaction times. [18] By using hydrogen peroxide and MIL-101 as catalysts, selective sulfoxidation of aryl sulfides becomes feasible. [4] Iron, copper or aluminium MOFs were active catalysts for the selective oxidation of xanthene to xanthone; however, the question as to whether or not catalytic activity might be due to leaching of metal ions from the nodes of the MOFs into solution was not addressed.…”

Section: Oa C H T U N G T R E N N U N G (Ohfh 2 O) 3 -A C H T U N Gmentioning

confidence: 99%

Pyrazolate‐Based Cobalt(II)‐Containing Metal–Organic Frameworks in Heterogeneous Catalytic Oxidation Reactions: Elucidating the Role of Entatic States for Biomimetic Oxidation Processes

Tonigold

Mavrandonakis

et al. 2011

Chemistry A European J

141

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Crystal structures of two metal-organic frameworks (MFU-1 and MFU-2) are presented, both of which contain redox-active Co(II) centres coordinated by linear 1,4-bis[(3,5-dimethyl)pyrazol-4-yl] ligands. In contrast to many MOFs reported previously, these compounds show excellent stability against hydrolytic decomposition. Catalytic turnover is achieved in oxidation reactions by employing tert-butyl hydroperoxide and the solid catalysts are easily recovered from the reaction mixture. Whereas heterogeneous catalysis is unambiguously demonstrated for MFU-1, MFU-2 shows catalytic activity due to slow metal leaching, emphasising the need for a deeper understanding of structure-reactivity relationships in the future design of redox-active metal-organic frameworks. Mechanistic details for oxidation reactions employing tert-butyl hydroperoxide are studied by UV/Vis and IR spectroscopy and XRPD measurements. The catalytic process accompanying changes of redox states and structural changes were investigated by means of cobalt K-edge X-ray absorption spectroscopy. To probe the putative binding modes of molecular oxygen, the isosteric heats of adsorption of O(2) were determined and compared with models from DFT calculations. The stabilities of the frameworks in an oxygen atmosphere as a reactive gas were examined by temperature-programmed oxidation (TPO). Solution impregnation of MFU-1 with a co-catalyst (N-hydroxyphthalimide) led to NHPI@MFU-1, which oxidised a range of organic substrates under ambient conditions by employing molecular oxygen from air. The catalytic reaction involved a biomimetic reaction cascade based on free radicals. The concept of an entatic state of the cobalt centres is proposed and its relevance for sustained catalytic activity is briefly discussed.

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Section: Oa C H T U N G T R E N N U N G (Ohfh 2 O) 3 -A C H T U N Gmentioning

confidence: 99%

Pyrazolate‐Based Cobalt(II)‐Containing Metal–Organic Frameworks in Heterogeneous Catalytic Oxidation Reactions: Elucidating the Role of Entatic States for Biomimetic Oxidation Processes

Tonigold

Mavrandonakis

et al. 2011

Chemistry A European J

141

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“…[25] It has been reported that the coordination environment [26] of the central metal ions in the copper complex has important influences on their catalytic activities in the oxidative coupling of DMP. In this case, the change in the coordination environment of the central copper ions may result in some change in the catalytic activity of the copper complexes.…”

Section: Anion Exchange Ofmentioning

confidence: 99%

3D Coordination Framework with Uncommon Two‐Fold Interpenetrated {3³⋅5⁹⋅6³}‐lcy Net and Coordinated Anion Exchange

Yang

et al. 2009

Chemistry A European J

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Unusual {3(3)5(9)6(3)}-lcy topology has been found in an uncommon 3D six-connected, two-fold interpenetrated {3(3)5(9)6(3)}-lcy net (illustrated). The coordinated SO(4) (2-) anions in this framework can undergo a full exchange with Cl(-) anions, in the course of which the crystals change color as shown. The process has a solvent-mediated rather than a solid-state mechanism.Reaction of tetrazole-1-acetic acid with CuSO(4)5H(2)O produces two novel 3D coordination frameworks: ([Cu(3)(mu(3)-OH)(eta(1):eta(1):eta(1):mu(3)-SO(4))(tza)(3)]3 CH(3)OHH(2)O}(n) (1; Htza=tetrazole-1-acetic acid) and {[Cu(4)(mu(2)-OH)(eta(2):eta(2):mu(4)-SO(4))(tta)(5)]3 H(2)O}(n) (2; Htta=tetrazole). Framework 1 is constructed from a trinuclear copper cluster [Cu(3)(mu(3)-OH)(eta(1):eta(1):eta(1):mu(3)-SO(4))] and displays a six-connected framework with uncommon {3(3)5(9)6(3)}-lcy topology. Framework 2 presents a complicated five-nodal (3,4,6)-connected net with (4(2)6)(34(2)5(2)7)(4(3)6(2)8)(3(2)4(8)5(3)6(2))(4(6)8(6)10(3)) topology. The eta(2):eta(2):mu(4)-SO(4) bridging mode in 2 has not been found in the reported coordination polymers. The coordinated SO(4) (2-) anions in 1 can be replaced completely when the solid polymer is treated with an aqueous methanolic solution containing Cl(-) anions. Detailed atomic force microscopy studies indicate a solvent-mediated rather than a solid-state mechanism for the exchange process.

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“…From previous studies, it has been proposed that the bridged coordination of DMP to dicopper(II) ions to form the active copper species is a key process in the polymerization of DMP to PPE [46][47]. Both of the electrophilicity [49] and coordination environment [50] of the central copper ions in the copper complex have important influences on their catalytic activities in the reaction progress. Obviously, the more electrophilic or the less steric congestive of the copper center is, the more higher the catalytic activity of the complex can be expected.…”

Section: Catalytic Properties Of the Complexesmentioning

confidence: 99%

Subtle role of counteranions in molecular construction: Structures and properties of novel Cu(II) coordination complexes with bis-(1-benzoimidazolymethylene)-(2,5-thiadiazoly)-disulfide

Liu

Hou

et al. 2009

Journal of Organometallic Chemistry

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Catalytic applications of CuII-containing MOFs based on N-heterocyclic ligand in the oxidative coupling of 2,6-dimethylphenol

Cited by 70 publications

References 47 publications

Pyrazolate‐Based Cobalt(II)‐Containing Metal–Organic Frameworks in Heterogeneous Catalytic Oxidation Reactions: Elucidating the Role of Entatic States for Biomimetic Oxidation Processes

Pyrazolate‐Based Cobalt(II)‐Containing Metal–Organic Frameworks in Heterogeneous Catalytic Oxidation Reactions: Elucidating the Role of Entatic States for Biomimetic Oxidation Processes

3D Coordination Framework with Uncommon Two‐Fold Interpenetrated {3³⋅5⁹⋅6³}‐lcy Net and Coordinated Anion Exchange

Subtle role of counteranions in molecular construction: Structures and properties of novel Cu(II) coordination complexes with bis-(1-benzoimidazolymethylene)-(2,5-thiadiazoly)-disulfide

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Catalytic applications of CuII-containing MOFs based on N-heterocyclic ligand in the oxidative coupling of 2,6-dimethylphenol

Cited by 70 publications

References 47 publications

Pyrazolate‐Based Cobalt(II)‐Containing Metal–Organic Frameworks in Heterogeneous Catalytic Oxidation Reactions: Elucidating the Role of Entatic States for Biomimetic Oxidation Processes

Pyrazolate‐Based Cobalt(II)‐Containing Metal–Organic Frameworks in Heterogeneous Catalytic Oxidation Reactions: Elucidating the Role of Entatic States for Biomimetic Oxidation Processes

3D Coordination Framework with Uncommon Two‐Fold Interpenetrated {33⋅59⋅63}‐lcy Net and Coordinated Anion Exchange

Subtle role of counteranions in molecular construction: Structures and properties of novel Cu(II) coordination complexes with bis-(1-benzoimidazolymethylene)-(2,5-thiadiazoly)-disulfide

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3D Coordination Framework with Uncommon Two‐Fold Interpenetrated {3³⋅5⁹⋅6³}‐lcy Net and Coordinated Anion Exchange