Metalloporphyrins as versatile catalysts for oxidation reactions and oxidative DNA cleavage

Meunier, Bernard

doi:10.1021/cr00014a008

Cited by 2,055 publications

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“…[1][2][3][4] Despite several industrial applications such as the oxidation of cyclohexane and p-xylene, which use O 2 as the oxidant and manganese or cobalt based catalysts, the development of practical oxidation catalysts and a thorough mechanistic understanding of alkane oxidation processes continue to provide great challenges in catalysis research. A number of different classes of alkane oxidation catalysts have been developed during the last 50 years, including the cobalt and manganese acetate catalyst systems used industrially, 5 the heme-based iron complexes containing porphyrin-type ligands used in nature, 6,7 polyoxometalates [8][9][10] and more recently, non-heme iron based catalyst systems. [11][12][13][14][15][16][17] The metal catalysts are typically combined with oxidants, which can have different oxo transfer abilities 18 , for example H 2 O 2 , O 2 , ClO -, PhIO, O 3 or N 2 O, whereby the first two oxidants are economically and environmentally the most attractive oxidants.…”

Section: Introductionmentioning

confidence: 99%

Towards robust alkane oxidation catalysts: electronic variations in non-heme iron(ii) complexes and their effect in catalytic alkane oxidation

et al. 2009

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A series of non-heme iron(II) bis(triflate) complexes containing linear and tripodal tetradentate ligands has been prepared. Electron withdrawing and electron donating substituents in the para position of the pyridine ligands as well the effect of pyrazine versus pyridine and sulphur or oxygen donors instead of nitrogen donors have been investigated. The electronic effects induced by these substituents influence the strength of the ligand field. UV-vis spectroscopy and magnetic susceptibility studies have been used to quantify these effects and VT 1 H and 19 F NMR spectroscopy as well as X-ray diffraction have been used to elucidate structural and geometrical aspects of these complexes. The catalytic properties of the iron(II) complexes as catalysts for the oxidation of cyclohexane with hydrogen peroxide have been evaluated. In the strongly oxidising environment required to oxidise alkanes, catalyst stability determines the overall catalytic efficiency of a given catalyst, which can be related to the ligand field strength and the basicity of the ligand and its propensity to undergo oxidation.2

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Section: Introductionmentioning

confidence: 99%

Towards robust alkane oxidation catalysts: electronic variations in non-heme iron(ii) complexes and their effect in catalytic alkane oxidation

et al. 2009

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“…The addition of a co -organic solvent in the reactional middle is indispensable; the authors do not work in an aqueous middle but in a mixture acetonitrile / buffer (1 / 3, V / V) or in a solution phosphates buffer / ethanol (80 / 20) or in a solution phosphates buffer / acetone 80 / 20 [6,7,8].…”

Section: Introductionmentioning

confidence: 99%

New Process of Catalytic Oxidation of Organic Pollutants from Water in Soft Conditions in Presence of Sulfonated Cobalt Phthalocyanines Supported on Activated Carbon

Goul

Mongi²

2017

Eco-Tech

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In the field of water treatment, catalytic oxidation has been developed around the Fenton reagent (hydrogen peroxide coupled with ferrous iron salt) but this oxidative system has drawbacks. In effect, this system only works in acidic pH. In addition, the Fenton reagent used at room temperature generally offers a partial oxidation of pollutants and is not accompanied by a significant removal of total organic carbon.The WPO process (Wet Peroxide Oxidation) that uses the catalytic activation of peroxide hydrogen at high temperature accelerates the kinetic of degradation reactions. But this method poses problems of cost due to the use of high temperatures reaching 140°C.In clean water, the oxygen is found mainly in the processes WAO (Wet Air Oxidation) which generates a huge investment because of high temperature and pressure (250 to 320 ° C -50 to 150 bar). This represents a major drawback in the industry.The catalytic oxidation reactions in the presence of métallophthalocyanines described in the literature involve KHSO 5 or H 2 O 2 which presents a disadvantage in a field of water depollution. Indeed, for the oxidation of trichlorophenol, adding an organic co-solvent is necessary: The reactions present the inconvenient to be conducted in a mixture acetonitrile / buffer (1 / 3, V / V) and not in an aqueous medium .Therefore, it appears that finding a method for oxidation catalysis involving transition metals and using oxygen under mild conditions of temperature and pressure is a particularly important challenge. During this work, we showed that the synthesis of a catalyst: phthaolocyanine cobalt sulfonated fixed on activated carbon is a simple process that takes place at room temperature. The action of these catalysts has been studied in the oxidation of hexanoic acid by oxygen in normal conditions (20 ° C, 1 atm.). We studied the reaction using two catalysts supported on activated carbon as grains, containing respectively 12 and 50 µmol / g cobalt. We showed that:https://doi.org/10.15626/Eco-Tech.2010.116Linnaeus ECO-TECH '10 Kalmar, Sweden, November 22-24, 2010 • the acid mineralization increases with the degree of grafting. In all cases, 97% of hexanoic acid is removed after 6h.• the behavior of catalysts has been studied through recycling. The catalyst with the lowest content in cobalt showed an increase of activity during the first four cycles. Such activity is stabilised with apparent values of the fall of total organic carbon (TOC) and chemical demand of oxygen (COD) of about 90 %. The increase of cobalt concentration enhances the rate of mineralization (expressed in relation to TOC eliminate d) from 45 % in the first cycle to 62 % at the third cycle. The loss of cobalt is very low. It is below 0,57 % after six cycles. We have also tested the catalytic action of this system in the succinic acid oxidation, oxalic acid and trichlorophenol. We obtain a quasi total fall of TOC and COD and an important rate of mineralization.All these consistent results, can validate this catalytic system. Especially s...

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“…1 The success of this pioneering work led to the synthesis of other metallo tetraarylporphyrins and the development of three generations of catalysts, which differ depending on the degree of substitution on the porphyrin ring. 2 Although the syntheses of the second and third generation porphyrins involve more expensive starting materials and are more time consuming, their improved robustness towards oxidative degradation and greater catalytic efficiency has led to detailed studies on oxidations catalyzed by these complexes. [2][3][4][5] A further approach to improve these systems has involved anchoring the complexes onto solid supports with the aim of allowing catalyst recovery and reuse.…”

Section: Introductionmentioning

confidence: 99%

“…2 Although the syntheses of the second and third generation porphyrins involve more expensive starting materials and are more time consuming, their improved robustness towards oxidative degradation and greater catalytic efficiency has led to detailed studies on oxidations catalyzed by these complexes. [2][3][4][5] A further approach to improve these systems has involved anchoring the complexes onto solid supports with the aim of allowing catalyst recovery and reuse. In this way, immobilization of the catalyst might provide a way to reduce the overall cost of using these compounds in synthesis.…”

Section: Introductionmentioning

confidence: 99%

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confidence: 99%

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Catalytic activity of halogenated iron porphyrins in alkene and alkane oxidations by iodosylbenzene and hydrogen peroxide

Guedes

Smith

Nascimento

et al. 2005

J. Braz. Chem. Soc.

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Uma ferro porfirina poli-clorada, Fe(PCl 8 )Cl, foi sintetizada e usada como catalisador em reações de oxidação de hidrocarbonetos por iodosilbenzeno e peróxido de hidrogênio, em solução e ancorado covalentemente na aminopropilsilica. Embora a Fe(PCl 8 )Cl tenha mostrado a mesma eficiência da ferro porfirina precursora, Fe(P)Cl, na epoxidação de alcenos, foi um catalisador mais eficiente na hidroxilação de alcanos por iodosilbenzeno, com preferência por carbonos secundários na oxidação do adamantano e primário na oxidação do pentano. Essa seletividade reflete o impedimento estéreo da espécie ferro-oxo ou, alternativamente, a grande reatividade do oxidante ativo gerado da Fe(PCl 8 )Cl. A Fe(PCl 8 )Cl ancorada mostrou baixa atividade catalítica quando comparada com o catalisador homogêneo e com a Fe(P)Cl ancorada. Peróxido de hidrogênio foi um oxidante pobre para este sistema. A excessiva substituição dos hidrogênios por grupos sacadores de elétrons na periferia do anel porfirínico dificulta a formação do intermediário ativo na reação de oxidação. O mecanismo alternativo de oxidação envolve a participação de radicais.A poly-halogenated iron porphyrin, Fe(PCl 8 )Cl, has been synthesised and used as a catalyst in hydrocarbon oxidations by iodosylbenzene and hydrogen peroxide both in solution and covalently bound to aminopropylated silica. The poly-chlorinated iron porphyrin shows the same efficiency of the related Fe(P)Cl, in the epoxidation of alkenes but higher efficiency in the hydroxylation of alkanes by iodosylbenzene, with increased preference for the oxidation of secondary carbon in adamantane and primary carbon in the oxidation of pentane. These selectivities may reflect the steric constraints around the oxo-iron species or, alternatively, it may arise from the greater reactivity of the active oxidant from Fe(PCl 8 )Cl. The supported iron(III) porphyrin showed lower activity as compared with the homogeneous analogue and the related supported Fe(P)Cl. The poly-chlorinated iron porpyrin is a poor catalyst with hydrogen peroxide. Excessive substitutuion by electron withdrawing groups on the porphyrin periphery eventually prohibits the formation of the key intermediate in catalytic oxidations. The alternative oxidation mechanism could involve radical participation.Keywords: poly-halogenated iron porphyrins, catalysis, supported catalysts, hydrocarbon oxidation IntroductionAbout 25 years have passed since an iron(III) porphyrin, [iron(III) tetraphenylporphyrin] with iodosylbenzene was first used as a functional model for cytochrome P-450 for hydrocarbon oxidation. 1 The success of this pioneering work led to the synthesis of other metallo tetraarylporphyrins and the development of three generations of catalysts, which differ depending on the degree of substitution on the porphyrin ring. 2 Although the syntheses of the second and third generation porphyrins involve more expensive starting materials and are more time consuming, their improved robustness towards oxidative degradation and greater catalytic efficiency...

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Metalloporphyrins as versatile catalysts for oxidation reactions and oxidative DNA cleavage

Cited by 2,055 publications

References 0 publications

Towards robust alkane oxidation catalysts: electronic variations in non-heme iron(ii) complexes and their effect in catalytic alkane oxidation

Towards robust alkane oxidation catalysts: electronic variations in non-heme iron(ii) complexes and their effect in catalytic alkane oxidation

New Process of Catalytic Oxidation of Organic Pollutants from Water in Soft Conditions in Presence of Sulfonated Cobalt Phthalocyanines Supported on Activated Carbon

Catalytic activity of halogenated iron porphyrins in alkene and alkane oxidations by iodosylbenzene and hydrogen peroxide

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