Non-heme iron polyazadentate complexes as catalysts for oxidations by H2O2: particular efficiency in aromatic hydroxylations and beneficial effects of a reducing agent

Balland, Véronique; Mathieu, Didier; Pons-Y-Moll, Nathalie; Bartoli, J. F.; Banse, Frédéric; Battioni, Pierrette; Girerd, Jean‐Jacques; Mansuy, Daniel

doi:10.1016/j.molcata.2004.01.015

Cited by 54 publications

(62 citation statements)

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“…Thus, the reaction pathway followed by this nonheme iron(III)-hydroperoxo complex appeared to deviate significantly from the one found for aromatic activation by iron-porphyrins, where phenol is usually the primary product [24,25]. [21]. Moreover, since the reaction leading to phenols appears to involve a non-unity KIE value this gives strong evidence of the formation of ketones as initial products that are converted to phenols at a later stage in the reaction.…”

Section: Introductionmentioning

confidence: 81%

“…In analogous work, Banse and coworkers [20] reported aromatic hydroxylation reactions by an iron(III)-hydroperoxo species (complex 1 in Scheme 1) with the pentadentate L 5 2 ligand (N-methyl- [21,22] and found it to react with benzene and anisole substrates efficiently. Interestingly, the use of [1,3,5-D 3 ]-benzene as a substrate probe [20], evidenced the occurrence of an NIH-shift whereby a hydrogen atom from the ipso-carbon position moved to the adjacent carbon atom, with a kinetic isotope effect (KIE) of k H /k D = 1.53 ± 0.16.…”

Section: Introductionmentioning

confidence: 99%

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Arene activation by a nonheme iron(III)–hydroperoxo complex: pathways leading to phenol and ketone products

2016

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Iron(III)-hydroperoxo complexes are found in various nonheme iron enzymes as catalytic cycle intermediates; however, little is known on their catalytic properties. Recent work of Banse and coworkers on a biomimetic nonheme iron(III)-hydroperoxo complex provided evidence of its involvement in reactivity with arenes. This contrasts the behavior of heme iron(III)-hydroperoxo complexes that are known to be sluggish oxidants. In order to gain insight into the reaction mechanism of the biomimetic iron(III)-hydroperoxo complex with arenes we performed a computational (density functional theory) study. The calculations show that iron(III)-hydroperoxo reacts with substrates via low free energies of activation that should be accessible at room temperature. Moreover, dominant ketone reaction product is observed as primary products rather than the thermodynamically more stable phenols. These product distributions are analyzed and the calculations show that charge interaction between the iron(III)-hydroxo group and the substrate in the intermediate state pushes the transferring proton to the metacarbon atom of substrate and guides the selectivity of ketone formation. These studies show that the relative ratio of ketone versus phenol as primary products can be affected by external interactions of the oxidant with substrate. Moreover, iron(III)-hydroperoxo complexes are shown to selectively give ketone products, whereas iron(IV)-oxo complexes will react with arenes to form phenols instead.

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Section: Introductionmentioning

confidence: 81%

Section: Introductionmentioning

confidence: 99%

Arene activation by a nonheme iron(III)–hydroperoxo complex: pathways leading to phenol and ketone products

2016

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“…Hydroxylation of anisole is used to produce methoxy phenols such as p-hydroxyanisole [264]. Hydroxylation of toluene and anisole could be carried out over zeolite-based catalyst [266,267], vanadium [264], and iron [268][269][270]. Hydroxylation of ethylbenzene and xylenes has received limited attention in literature.…”

Section: Potential Existing Technologies and New Considerations For Vmentioning

confidence: 99%

Utilization of Volatile Organic Compounds as an Alternative for Destructive Abatement

et al. 2015

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Abstract:The treatment of volatile organic compounds (VOC) emissions is a necessity of today. The catalytic treatment has already proven to be environmentally and economically sound technology for the total oxidation of the VOCs. However, in certain cases, it may also become economical to utilize these emissions in some profitable way. Currently, the most common way to utilize the VOC emissions is their use in energy production. However, interesting possibilities are arising from the usage of VOCs in hydrogen and syngas production. Production of chemicals from VOC emissions is still mainly at the research stage. However, few commercial examples exist. This review will summarize the commercially existing VOC utilization possibilities, present the utilization applications that are in the research stage and introduce some novel ideas related to the catalytic utilization possibilities of the VOC emissions. In general, there exist a vast number of possibilities for VOC OPEN ACCESSCatalysts 2015, 5 1093 utilization via different catalytic processes, which creates also a good research potential for the future.

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“…For example, toluene was oxidized by iron(II) complexes bearing hexa-, penta-or tetra-azadentate ligands -H 2 O 2 system to mixture of isomeric cresols, benzyl alcohol and benzaldehyde. [40] Oxidation of toluene performed by metalloporphyrin systems has often resulted in the mixture of products of benzylic and aromatic oxidation. [41] In order to evaluate the reactivity of µ-nitrido bridged diiron complexes toward oxidation of aliphatic C-H vs. aromatic oxidation we have studied the oxidation of toluene and p-xylene by t BuOOH.…”

Section: Oxidation Of Alkylaromatic Compoundsmentioning

confidence: 99%

µ-Nitrido Bridged Diiron Phthalocyanines: Old Complexes for New Catalytic Applications

Kudrik¹,

Sorokin²

2011

MHC

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Non-heme iron polyazadentate complexes as catalysts for oxidations by H2O2: particular efficiency in aromatic hydroxylations and beneficial effects of a reducing agent

Cited by 54 publications

References 18 publications

Arene activation by a nonheme iron(III)–hydroperoxo complex: pathways leading to phenol and ketone products

Arene activation by a nonheme iron(III)–hydroperoxo complex: pathways leading to phenol and ketone products

Utilization of Volatile Organic Compounds as an Alternative for Destructive Abatement

µ-Nitrido Bridged Diiron Phthalocyanines: Old Complexes for New Catalytic Applications

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