Metalloporphyrins as catalysts in the decomposition of cyclohexyl hydroperoxide

Hansen, C. B.; Drenth, W.

doi:10.1007/bf00769309

Cited by 10 publications

(2 citation statements)

References 37 publications

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“…It was determined that the adsorption ratios indane/indanol, indane/indanone or indane/(indanol + indanone) are higher in the adsorption experiments of MIL-101(Cr) with respect to MIL-101(Fe), thus, lending support to differences in adsorption preferences as the possible origin of the selectivity differences observed for both MOFs. In addition, it could be that these differences could derive from the different 1-indanyl hydroperoxide stability in both MOFs (compare panels b and c of Figure and Figure S3b,3Sc) as consequence of the higher ability of Cr 3+ to decompose this intermediate, as compared to Fe 2+ / 3+ ions. , …”

Section: Resultsmentioning

confidence: 99%

“…In addition, it could be that these differences could derive from the different 1-indanyl hydroperoxide stability in both MOFs (compare panels b and c of Figure 1 and Figure S3b,3Sc) as consequence of the higher ability of Cr 3+ to decompose this intermediate, as compared to Fe 2+ / 3+ ions. 45,46 Stability of MIL-101(Cr) as catalyst was determined by measuring the catalytic activity upon consecutive reuses as well as by analytical measurements of ion metals in the solution and by determining the crystallinity of the solid. It was observed that in four consecutive uses, the time conversion plot (Figure 2a) and the conversion/selectivity curve (Figure 2b) were coincident, thus proving that the catalytic activity does not decrease upon reuse.…”

Section: Acs Catalysismentioning

confidence: 99%

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MIL-101 as Reusable Solid Catalyst for Autoxidation of Benzylic Hydrocarbons in the Absence of Additional Oxidizing Reagents

et al. 2015

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Materiaux de l'Institute Lavosier-101 (MIL-101) promotes benzylic oxidation of hydrocarbons exclusively by molecular oxygen in the absence of any other oxidizing reagent or initiator. Using indane as model compound, the selectivity toward the wanted ol/one mixture is higher for MIL-101(Cr) (87% selectivity at 30% conversion) than for MIL-101(Fe) (71% selectivity at 30% conversion), a fact that was associated with the preferential adsorption of indane within the pore system. Product distribution and quenching experiments with 2,2,6,6-tetramethyl-1-piperidinyloxy, benzoic acid, and dimethylformamide show that the reaction mechanism is a radical chain autoxidation of the benzylic positions by molecular oxygen, and the differences in selectivity have been attributed to the occurrence of the autoxidation process inside or outside the metal organic framework pores. MIL-101 is reusable, does not leach metals to the solution, and maintains the crystal structure during the reaction. The scope of the benzylic oxidation was expanded to other benzylic compounds including ethylbenzene, n-butylbenzene, iso-butylbenzene, 1bromo-4-butylbenzene, sec-butylbenzene, and cumene.

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Section: Resultsmentioning

confidence: 99%

Section: Acs Catalysismentioning

confidence: 99%

MIL-101 as Reusable Solid Catalyst for Autoxidation of Benzylic Hydrocarbons in the Absence of Additional Oxidizing Reagents

et al. 2015

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Mild Peroxidative Oxidation of Cyclohexane Catalyzed by Mono‐, Di‐, Tri‐, Tetra‐ and Polynuclear Copper Triethanolamine Complexes

Kirillov¹,

Kopylovich²,

Kirillova³

et al. 2006

Adv Synth Catal

166

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Abstract:The mono-, di-, tri-, tetra-and polynuclear copper (II) (5), respectively, are highly active and selective catalysts or catalyst precursors for the peroxidative oxidation of cyclohexane, in acetonitrile, to a cyclohexanol and cyclohexanone mixture, by aqueous hydrogen peroxide in acidic medium (liquid biphasic catalysis) at room temperature and atmospheric pressure. The effects on the catalytic activity of various factors, e.g., the relative amounts of cyclohexane, oxidant, catalyst, solvent and nitric acid, reaction time, catalyst recycling and impact of both carbon-and oxygen-centred radical traps (supporting mainly radical mechanisms) were investigated and allowed us to achieve yields and TONs up to ca. 39% and 380, respectively, corresponding to the most active copper systems so far reported for the oxidation of cyclohexane under mild conditions. The catalysts can be reused for recycling and, at least complex 4 maintains almost the same level of activity even after five reaction cycles. The preparation of the new complexes 1, 2b and 2c by self-assembly at room temperature, and their full characterization by IR spectroscopy, FAB-MS þ , elemental and X-ray diffraction structural (for 1 and 2c) analyses are also reported.

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Catalytic oxidations using ruthenium porphyrins

Ezhova

James

2003

Advances in Catalytic Activation of Dioxygen by Metal Complexes

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Metalloporphyrins as catalysts in the decomposition of cyclohexyl hydroperoxide

Cited by 10 publications

References 37 publications

MIL-101 as Reusable Solid Catalyst for Autoxidation of Benzylic Hydrocarbons in the Absence of Additional Oxidizing Reagents

MIL-101 as Reusable Solid Catalyst for Autoxidation of Benzylic Hydrocarbons in the Absence of Additional Oxidizing Reagents

Mild Peroxidative Oxidation of Cyclohexane Catalyzed by Mono‐, Di‐, Tri‐, Tetra‐ and Polynuclear Copper Triethanolamine Complexes

Catalytic oxidations using ruthenium porphyrins

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