Mechanistic Tuning of Hydrocarbon Oxidations with H2O2, Catalyzed by Hexacoordinate Ferrous Complexes

• Published in: European journal of inorganic chemistry 2004-08, Vol.2004 (15), p.3163-3171
• Main Authors: Mekmouche, Yasmina, Ménage, Stéphane, Pécaut, Jacques, Lebrun, Colette, Reilly, Lee, Schuenemann, Volker, Trautwein, Alfred, Fontecave, Marc
• Format: Article
• Language: English
• Subjects: Hydrogen peroxide; Iron catalysts; Monooxygenase; Non-heme iron; Oxidation
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.200300926

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)