Sulfide oxidation by hydrogen peroxide catalyzed by iron complexes: two metal centers are better than one.
Peroxoiron species have been proposed to be involved in catalytic cycles of iron-dependent oxygenases and in some cases as the active intermediates during oxygen-transfer reactions. The catalytic properties of a mononuclear iron complex, [Fe(II)(pb)(2)(CH(3)CN)(2)] (pb=(-)4,5-pinene-2,2'-bipyridine), have been compared to those of its related dinuclear analogue. Each system generates specific peroxo adducts, which are responsible for the oxidation of sulfides to sulfoxides. The dinuclear catalyst was found to be more reactive and (enantio)selective than its mononuclear counterpart, suggesting that a second metal site affords specific advantages for stereoselective catalysis. These results might help for the design of future enantioselective iron catalysts.
Mekmouche
Yasmina
Y
Laboratoire de Chimie et Biochimie, Centres Rédox Biologiques, Université Joseph Fourier/DBMS/CEA, UMR CNRS 5047 Grenoble, 17 rue des Martyrs, 38054 Grenoble Cédex 9, France.
Hummel
Helga
H
Ho
Raymond Y N
RY
Que
Lawrence
L
Schünemann
Volker
V
Thomas
Fabrice
F
Trautwein
Alfred X
AX
Lebrun
Colette
C
Gorgy
Karine
K
Leprêtre
Jean-Claude
JC
Collomb
Marie-Noëlle
MN
Deronzier
Alain
A
Fontecave
Marc
M
Ménage
Stéphane
S
D002384:Catalysis; D006861:Hydrogen Peroxide / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D013440:Sulfides / Q000737:chemistry*; D013454:Sulfoxides / Q000737:chemistry
D013440:Sulfides; D013454:Sulfoxides; D006861:Hydrogen Peroxide; D007501:Iron