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Robust iron coordination complexes with N-based neutral ligands as efficient fenton-like catalysts at neutral pH

The homogeneous Fenton-like oxidation of organic substrates in water with hydrogen peroxide, catalyzed by six different metal coordination complexes with N-based neutral ligands, was studied at ambient conditions and initial pH 7, employing hydrogen peroxide as the terminal oxidant. At low catalyst concentration, the catalytic oxidative depletion of toluene achieved by selected catalysts was much more efficient than that obtained by the Fenton reagent at pH 3. The influence of pH, the water matrix and the catalyst/hydrogen peroxide concentration were investigated for the oxidation of toluene employing [FeCl2(bpmcn)] (1, bpmcn = N,N′-bis(2-pyridylmethyl)-N, N′-dimethyl-trans-1,2-diaminocyclohexane), the most efficient catalyst of the series. Moreover, the evolution of catalysts [FeCl2(bpmcn)] (1) and [Fe(OTf)2(Pytacn)] (3, Pytacn = 1-(2-pyridylmethyl)-4,7-dimethyl- 1,4,7-triazacyclononane, OTf = trifluoromethanesulfonate anion) during the course of the reaction was also studied by electrospray ionization mass spectrometry (ESI-MS). The oxidation products derived from toluene oxidation were also analyzed. A plausible mechanism of toluene degradation using [FeCl2(bpmcn)] (1) and [Fe(OTf)2(Pytacn)] (3) as catalysts was proposed, which involves the coexistence of a metal-based path, analogous to that operating in organic media where substrate oxidation is executed by an iron(V)-oxo-hydroxo species, in parallel to a Fenton-type process where hydroxyl radicals are formed

M.C. thanks the European Research Council for a Starting Grant Fellowship (ERC-2009-StG-239910), MINECO of Spain (CTQ2012-37420-C02-01/BQU, Consolider-Ingenio CSD2010-00065) and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637, and ICREA Academia Award). A.C. thanks the European Commission for a Career Integration Grant (FP7-PEOPLE-2011-CIG-303522). Ministerio de Ciencia e Innovacion (Spain) is acknowledged for financial support with the project SIRENA (CTQ2011-24114), for a Juan de la Cierva contract to R.G.-O. (JCI-2010-07104) and for a Ramon y Cajal contract to A. C. (RYC-2011-08683). Mr. Z. Codola is acknowledged for his help with the experimental setup for the determination of the overpressure generated into the reactors

info:eu-repo/grantAgreement/MINECO//CTQ2012-37420-C02-01/ES/DISEÑO BIOINSPIRADO DE CATALIZADORES PARA LA OXIDACION DE ENLACES C-H, C=C Y AGUA/

American Chemical Society (ACS)

Manager: European Research Council
Ministerio de Economía y Competitividad (Espanya)
Ministerio de Ciencia e Innovación (Espanya)
Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca
Author: Canals Guimerà, Maite
González Olmos, Rafael
Costas Salgueiro, Miquel
Company Casadevall, Anna
Abstract: The homogeneous Fenton-like oxidation of organic substrates in water with hydrogen peroxide, catalyzed by six different metal coordination complexes with N-based neutral ligands, was studied at ambient conditions and initial pH 7, employing hydrogen peroxide as the terminal oxidant. At low catalyst concentration, the catalytic oxidative depletion of toluene achieved by selected catalysts was much more efficient than that obtained by the Fenton reagent at pH 3. The influence of pH, the water matrix and the catalyst/hydrogen peroxide concentration were investigated for the oxidation of toluene employing [FeCl2(bpmcn)] (1, bpmcn = N,N′-bis(2-pyridylmethyl)-N, N′-dimethyl-trans-1,2-diaminocyclohexane), the most efficient catalyst of the series. Moreover, the evolution of catalysts [FeCl2(bpmcn)] (1) and [Fe(OTf)2(Pytacn)] (3, Pytacn = 1-(2-pyridylmethyl)-4,7-dimethyl- 1,4,7-triazacyclononane, OTf = trifluoromethanesulfonate anion) during the course of the reaction was also studied by electrospray ionization mass spectrometry (ESI-MS). The oxidation products derived from toluene oxidation were also analyzed. A plausible mechanism of toluene degradation using [FeCl2(bpmcn)] (1) and [Fe(OTf)2(Pytacn)] (3) as catalysts was proposed, which involves the coexistence of a metal-based path, analogous to that operating in organic media where substrate oxidation is executed by an iron(V)-oxo-hydroxo species, in parallel to a Fenton-type process where hydroxyl radicals are formed
M.C. thanks the European Research Council for a Starting Grant Fellowship (ERC-2009-StG-239910), MINECO of Spain (CTQ2012-37420-C02-01/BQU, Consolider-Ingenio CSD2010-00065) and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637, and ICREA Academia Award). A.C. thanks the European Commission for a Career Integration Grant (FP7-PEOPLE-2011-CIG-303522). Ministerio de Ciencia e Innovacion (Spain) is acknowledged for financial support with the project SIRENA (CTQ2011-24114), for a Juan de la Cierva contract to R.G.-O. (JCI-2010-07104) and for a Ramon y Cajal contract to A. C. (RYC-2011-08683). Mr. Z. Codola is acknowledged for his help with the experimental setup for the determination of the overpressure generated into the reactors
Format: application/pdf
Document access: http://hdl.handle.net/10256/10180
Language: eng
Publisher: American Chemical Society (ACS)
Collection: info:eu-repo/semantics/altIdentifier/doi/10.1021/es401602t
info:eu-repo/semantics/altIdentifier/issn/0013-936X
info:eu-repo/semantics/altIdentifier/eissn/1520-5851
MICINN/PN 2010-2016/CSD2010-00065
info:eu-repo/grantAgreement/MICINN//CTQ2011-24114/ES/ELIMINACION DE SILOXANOS EN LA RECUPERACION ENERGETICA DE BIOGAS DE DEPURADORA: ADSORCION Y REGENERACION MEDIANTE PROCESOS DE OXIDACION AVANZADA/
AGAUR/2009-2014/2009 SGR-637
info:eu-repo/grantAgreement/MICINN//JCI-2010-07104/ES/JCI-2010-07104/
info:eu-repo/grantAgreement/MICINN//RYC-2011-08683/ES/RYC-2011-08683/
info:eu-repo/grantAgreement/EC/FP7/303522/EU/Key insights into oxidation chemistry through synthetic systems: N2O activation with first-row transition-metals and O2 activation in heterobimetallic Fe-Ni systems/NEWOXMET
info:eu-repo/grantAgreement/EC/FP7/239910/EU/Bio-inspired Design of Catalysts for Selective Oxidations of C-H and C=C Bonds/BIDECASEOX
Is part of: info:eu-repo/grantAgreement/MINECO//CTQ2012-37420-C02-01/ES/DISEÑO BIOINSPIRADO DE CATALIZADORES PARA LA OXIDACION DE ENLACES C-H, C=C Y AGUA/
Rights: Tots els drets reservats
Subject: Oxidació
Oxidation
Catalitzadors
Catalysts
Aigua oxigenada
Hydrogen peroxide
Reaccions químiques
Chemical reactions
Title: Robust iron coordination complexes with N-based neutral ligands as efficient fenton-like catalysts at neutral pH
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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