Direct hydroxylation of benzene to phenol by nitrous oxide on amorphous aluminium-iron binary phosphates

Navarro, R.; Lopez-Pedrajas, S.; Luna, Diego; Marinas, J. M.; Bautista, Felipa M.

doi:10.1016/j.apcata.2013.08.043

Cited by 27 publications

(27 citation statements)

References 36 publications

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“…The electrochemical data are given in Table 2. On the basis of previous reports on [(μ-pdt){Fe(CO) 3 II Fe I oxidation becomes more accessible by approximately 470 mV, as compared to 1. According to the related literature, these redox events are all one-electron processes.…”

Section: Electrochemistrymentioning

confidence: 93%

“…After removal of the solvent by distillation, the products were purified by chromatography on successive silica columns with hexane as the eluent (4.2 g, 32.8 %). Single crystals suitable for X-ray crystallographic analysis were obtained by slow diffusion of hexane into CH 2 3 (1 equiv., 131 mg, 0.50 mmol) in CH 3 CN (10 mL) was then added and subsequently heated at 80°C for 5 h. After removal of CH 3 CN in a vacuum, the products were purified by chromatography on successive silica columns monitored by IR spectroscopy. First, hexane was used as the eluent to remove 1.…”

Section: Methodsmentioning

confidence: 99%

“…DFT calculations suggest that the Fe-Fe bond in [(μ-pdt){Fe(CO) 3 } 2 ] or its derivatives is thermodynamically favored to be oxidized to the μ-oxido product Fe II -μ-O-Fe II . On the basis of these results and the above-mentioned conclusion that the hydroxylation reactivity of the diiron complexes stems from the oxygenation of the Fe-Fe bond, we assumed that the Fe…”

Section: Theoretical Detailsmentioning

confidence: 99%

“…Theoretical calculations similar to literature reports [34] were carried out to compare metal-based and sulfur-based oxygenation of the active-site paradigm of [(μ-dmedt){Fe(CO) 3 To support our choice for the function and the basis set, the DFT calculations were performed for isolated complexes 1, 1-PPh 3 , and 1-O first, for which the experimental geometrical parameters are available in this article. The optimized geometrical parameters ( Figures S1-S3, Tables S2-S7) are in good agreement with the experimental data obtained by X-ray diffraction analyses (deviations Ͻ5 %), which confirms the reliability of the calculation method used for describing the present system.…”

Section: -μ-O-fementioning

confidence: 99%

“…The direct catalytic hydroxylation of aromatic compounds to phenols under mild conditions remains a major challenge in industrial and synthetic chemistry [1][2][3][4][5] and has attracted considerable interest, the ultimate goal of which is to find a substitute for the multistep and environmentally hazardous process used today. [6] Among various catalysts for the selective hydroxylation of aromatic compounds, iron-based catalysts have been an active research area for many years, [7][8][9][10] because they catalyze a number of chemically challenging oxidative processes with high selectivity and reaction rates, [11,12] and because iron is geologically abundant.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Characterization of Bio‐Inspired Diiron Complexes and Their Catalytic Activity for Direct Hydroxylation of Aromatic Compounds

et al. 2015

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Three [FeFe]‐hydrogenase model complexes [(μ‐dmedt){Fe(CO)3}2] [1; dmedt = SCH(CH3)CH(CH3)S], [(μ‐dmedt){Fe(CO)3}{Fe (CO)2PPh3}] (1‐PPh3), and [(μ‐dmest){Fe(CO)3}2] [1‐O; dmest = SCH(CH3)CH(CH3)S(O)], 1‐O were synthesized and characterized. These model complexes, which are generally used as the functional biomimics of the hydrogen‐producing dinuclear active site in [FeFe]‐hydrogenase, were used as efficient catalysts for the selective hydroxylation of aromatic compounds to phenols under mild conditions. Because both the dithiolato‐sulfur site and the Fe–Fe bond in the model complexes were possible active oxidation sites, DFT calculations were used to investigate the oxygenated products, that is, the S‐oxygenated products or the Fe‐oxygenated forms of the model complexes, which may be involved in the catalytic cycle. The experimental and computational results indicate that the thermodynamically favored Fe‐oxygenated intermediates dominate the hydroxylation of the aromatic compounds. A possible mechanism for the hydroxylation is also proposed.

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Section: Electrochemistrymentioning

confidence: 93%

Section: Methodsmentioning

confidence: 99%

Section: Theoretical Detailsmentioning

confidence: 99%

Section: -μ-O-fementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Synthesis and Characterization of Bio‐Inspired Diiron Complexes and Their Catalytic Activity for Direct Hydroxylation of Aromatic Compounds

et al. 2015

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Facile and Direct Hydroxylation of Benzene to Phenol over Graphene‐Based Catalysts: Integrated Utilization of Greenhouse Nitrous Oxide

Zhu

Yun

Wang

et al. 2018

Advcd Theory and Sims

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Graphene catalysis has recently emerged as a focus and herein a novel and highly efficient process is computationally designed using graphene-based catalysts that integrates the utilization of greenhouse nitrous oxide (N 2 O) as oxidant. The ground-state pristine graphene is not catalytically active for benzene hydroxylation, and doping and photocatalysis through excitations are employed to improve the catalyst systems, while both strategies exhibit limited effects. A combination of Be-doping and photocatalysis through excitations results in encouraging changes, where all energy barriers are moderate, so that the whole catalytic processes proceed facilely at mild conditions. Graphene materials, especially Be-and O-doped ones, are good photocatalysts due to the low excitation energies. Mechanistic studies indicate that the active sites of the excited-state graphene, whether pristine or doped, are oxygen anion radical (O −• ) and distinct from the epoxide species for the ground state; in addition, Be-doping pronouncedly reduces the excitation energies and enhances the interactions with the active-site O species, which further show strong stabilization effects to transition states and reduce substantially the energy barriers.

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Insight into the gas‐phase glycerol dehydration on transition metal modified aluminium phosphates and zeolites

Lopez-Pedrajas

Estévez

Blanco-Bonilla

et al. 2017

J of Chemical Tech & Biotech

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BACKGROUND: The production of biodiesel has notably increased in recent years, with glycerol as the main by-product, an important raw material in the production of value-added products. Those obtained by dehydration are especially important. RESULTS: Gas phase dehydration of glycerol has been tested on mesoporous AlPO 4 and modified AlPO 4 , with a small amount (1 wt%) of a transition metal (Co, Cu, Cr, Fe), calcined at 450 ∘ C and 650 ∘ C, and compared with some commercial zeolites (HZSM and HY). All the catalysts were active in the reaction, the phosphates showing better catalytic behaviour than the zeolites. The main products of the reaction were acrolein and hydroxyacetone. CONCLUSIONS:The positive effect of metal on the catalytic behaviour of AlPO 4 in the dehydration has been verified, attaining the maximum yield to acrolein (54%) on AlCoPO650 with 50 mg of catalyst and 280 ∘ C of reaction temperature. Furthermore, the phosphates did not suffer deactivation after 22 h reaction, whereas the zeolites suffered a strong loss of activity (around 70%) due to blockage of the micropores by coke. Moreover, the yield to acrolein decreased with time, while the yield to hydroxyacetone increased. An E 2 mechanism for the acrolein formation and E 1 for the hydroxyacetone formation have been proposed.

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Direct hydroxylation of benzene to phenol by nitrous oxide on amorphous aluminium-iron binary phosphates

Cited by 27 publications

References 36 publications

Synthesis and Characterization of Bio‐Inspired Diiron Complexes and Their Catalytic Activity for Direct Hydroxylation of Aromatic Compounds

Synthesis and Characterization of Bio‐Inspired Diiron Complexes and Their Catalytic Activity for Direct Hydroxylation of Aromatic Compounds

Facile and Direct Hydroxylation of Benzene to Phenol over Graphene‐Based Catalysts: Integrated Utilization of Greenhouse Nitrous Oxide

Insight into the gas‐phase glycerol dehydration on transition metal modified aluminium phosphates and zeolites

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