TY - JOUR
T1 - Mechanistic tuning of hydrocarbon oxidations with H2O 2, catalyzed by hexacoordinate ferrous complexes
AU - Mekmouche, Yasmina
AU - Ménage, Stéphane
AU - Pécaut, Jacques
AU - Lebrun, Colette
AU - Reilly, Lee
AU - Schuenemann, Volker
AU - Trautwein, Alfred
AU - Fontecave, Marc
PY - 2004/8/6
Y1 - 2004/8/6
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=4544327625&partnerID=8YFLogxK
U2 - 10.1002/ejic.200300926
DO - 10.1002/ejic.200300926
M3 - Journal articles
AN - SCOPUS:4544327625
SP - 3163
EP - 3171
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
SN - 1434-1948
IS - 15
ER -