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Mechanistic Tuning of Hydrocarbon Oxidations with H 2 O 2 , Catalyzed by Hexacoordinate Ferrous Complexes
Author(s) -
Mekmouche Yasmina,
Ménage Stéphane,
Pécaut Jacques,
Lebrun Colette,
Reilly Lee,
Schuenemann Volker,
Trautwein Alfred,
Fontecave Marc
Publication year - 2004
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200300926
Subject(s) - chemistry , hexacoordinate , catalysis , medicinal chemistry , ferrous , ligand (biochemistry) , radical , metal , lability , reaction mechanism , bond cleavage , hydrocarbon , redox , diamine , reaction intermediate , stereochemistry , inorganic chemistry , polymer chemistry , organic chemistry , biochemistry , receptor , silicon
A comparison of the catalytic properties of a series of Fe II LXY complexes on oxidation reactions with H 2 O 2 , [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 CH 3 CN) 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 CH 3 CN ligands (X = Y = CH 3 CN) 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 = CH 3 CN), 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)