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Mechanistic Tuning of Hydrocarbon Oxidations with H2O2, Catalyzed by Hexacoordinate Ferrous Complexes
A comparison of the catalytic properties of a series of FeIILXY complexes on oxidation reactions with H2O2, [L = N,N′‐bis(pyridin‐2‐yl‐methyl)‐N,N′‐bis(3,4,5‐trimethoxybenzyl)ethane‐1,2‐diamine] indicates that the lability of the X and Y ligands (Cl− or CH3CN) determines the nature of the oxidation...
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Published in: | European journal of inorganic chemistry 2004-08, Vol.2004 (15), p.3163-3171 |
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container_title | European journal of inorganic chemistry |
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creator | Mekmouche, Yasmina Ménage, Stéphane Pécaut, Jacques Lebrun, Colette Reilly, Lee Schuenemann, Volker Trautwein, Alfred Fontecave, Marc |
description | A comparison of the catalytic properties of a series of FeIILXY complexes on oxidation reactions with H2O2, [L = N,N′‐bis(pyridin‐2‐yl‐methyl)‐N,N′‐bis(3,4,5‐trimethoxybenzyl)ethane‐1,2‐diamine] indicates that the lability of the X and Y ligands (Cl− or CH3CN) determines the nature of the oxidation pathway. The absence of a labile site in the complex, i.e. when X = Y = Cl−, causes the reaction to proceed via a Fenton pathway (generation of hydroxyl radicals, exclusively). The presence of two labile CH3CN ligands (X = Y = CH3CN) allows the catalysis to proceed through a metal‐based mechanism, whereas in the case of a complex with only one labile ligand (X = Cl− and Y = CH3CN), the reaction is less controlled by the metal. We wish to emphasize that the cleavage of the O−O bond in the Fe−OOH moeity, a key intermediate in the reaction, is different in the last two cases. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) |
doi_str_mv | 10.1002/ejic.200300926 |
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The absence of a labile site in the complex, i.e. when X = Y = Cl−, causes the reaction to proceed via a Fenton pathway (generation of hydroxyl radicals, exclusively). The presence of two labile CH3CN ligands (X = Y = CH3CN) allows the catalysis to proceed through a metal‐based mechanism, whereas in the case of a complex with only one labile ligand (X = Cl− and Y = CH3CN), the reaction is less controlled by the metal. We wish to emphasize that the cleavage of the O−O bond in the Fe−OOH moeity, a key intermediate in the reaction, is different in the last two cases. (© Wiley‐VCH Verlag GmbH & Co. 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KGaA, 69451 Weinheim, Germany, 2004)</description><subject>Hydrogen peroxide</subject><subject>Iron catalysts</subject><subject>Monooxygenase</subject><subject>Non-heme iron</subject><subject>Oxidation</subject><issn>1434-1948</issn><issn>1099-0682</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2004</creationdate><recordtype>article</recordtype><recordid>eNo9kM9PwjAYhhujiYhePfcPcNpfW9ujWYBhpnDAeGzarZPiWEk3wuZfLwTD6Xu_5H3ewwPAI0bPGCHyYjeueCYIUYQkSa7ACCMpI5QIcn3MjLIISyZuwV3bbtCpRpMRsO-2WOvGtZ0r4GrfuOYb-gpmQxl8oYPxDVz0rtSd800LD65bw4wsyBNMdafr4deW0Awws70uvA-la3Rn4dSG4PctTP12V9vetvfgptJ1ax_-7xh8TierNIvyxWyevuaRw5wmkSS84ibGlUDaSK4xs4QKbY0WcVmKAmNCYiYqLHjMGaZCGBOzpEDS2FgyRsdAnncPrraD2gW31WFQGKmTIXUypC6G1ORtnl6-Ixud2aML219YHX5UwimP1dfHTIlZvpyJZa4y-gcY1mwh</recordid><startdate>200408</startdate><enddate>200408</enddate><creator>Mekmouche, Yasmina</creator><creator>Ménage, Stéphane</creator><creator>Pécaut, Jacques</creator><creator>Lebrun, Colette</creator><creator>Reilly, Lee</creator><creator>Schuenemann, Volker</creator><creator>Trautwein, Alfred</creator><creator>Fontecave, Marc</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><scope>BSCLL</scope></search><sort><creationdate>200408</creationdate><title>Mechanistic Tuning of Hydrocarbon Oxidations with H2O2, Catalyzed by Hexacoordinate Ferrous Complexes</title><author>Mekmouche, Yasmina ; Ménage, Stéphane ; Pécaut, Jacques ; Lebrun, Colette ; Reilly, Lee ; Schuenemann, Volker ; Trautwein, Alfred ; Fontecave, Marc</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-i1736-927f7b51f80ab97a14e238aeba85dd8c1122548f1875741388bb546c09be59443</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2004</creationdate><topic>Hydrogen peroxide</topic><topic>Iron catalysts</topic><topic>Monooxygenase</topic><topic>Non-heme iron</topic><topic>Oxidation</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Mekmouche, Yasmina</creatorcontrib><creatorcontrib>Ménage, Stéphane</creatorcontrib><creatorcontrib>Pécaut, Jacques</creatorcontrib><creatorcontrib>Lebrun, Colette</creatorcontrib><creatorcontrib>Reilly, Lee</creatorcontrib><creatorcontrib>Schuenemann, Volker</creatorcontrib><creatorcontrib>Trautwein, Alfred</creatorcontrib><creatorcontrib>Fontecave, Marc</creatorcontrib><collection>Istex</collection><jtitle>European journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Mekmouche, Yasmina</au><au>Ménage, Stéphane</au><au>Pécaut, Jacques</au><au>Lebrun, Colette</au><au>Reilly, Lee</au><au>Schuenemann, Volker</au><au>Trautwein, Alfred</au><au>Fontecave, Marc</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Mechanistic Tuning of Hydrocarbon Oxidations with H2O2, Catalyzed by Hexacoordinate Ferrous Complexes</atitle><jtitle>European journal of inorganic chemistry</jtitle><addtitle>Eur. J. Inorg. Chem</addtitle><date>2004-08</date><risdate>2004</risdate><volume>2004</volume><issue>15</issue><spage>3163</spage><epage>3171</epage><pages>3163-3171</pages><issn>1434-1948</issn><eissn>1099-0682</eissn><abstract>A comparison of the catalytic properties of a series of FeIILXY complexes on oxidation reactions with H2O2, [L = N,N′‐bis(pyridin‐2‐yl‐methyl)‐N,N′‐bis(3,4,5‐trimethoxybenzyl)ethane‐1,2‐diamine] indicates that the lability of the X and Y ligands (Cl− or CH3CN) determines the nature of the oxidation pathway. The absence of a labile site in the complex, i.e. when X = Y = Cl−, causes the reaction to proceed via a Fenton pathway (generation of hydroxyl radicals, exclusively). The presence of two labile CH3CN ligands (X = Y = CH3CN) allows the catalysis to proceed through a metal‐based mechanism, whereas in the case of a complex with only one labile ligand (X = Cl− and Y = CH3CN), the reaction is less controlled by the metal. We wish to emphasize that the cleavage of the O−O bond in the Fe−OOH moeity, a key intermediate in the reaction, is different in the last two cases. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><doi>10.1002/ejic.200300926</doi><tpages>9</tpages></addata></record> |
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source | Wiley-Blackwell Read & Publish Collection |
subjects | Hydrogen peroxide Iron catalysts Monooxygenase Non-heme iron Oxidation |
title | Mechanistic Tuning of Hydrocarbon Oxidations with H2O2, Catalyzed by Hexacoordinate Ferrous Complexes |
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