Epoxidations catalyzed by manganese(V) oxo and imido complexes: role of the oxidant-Mn-oxo (imido) intermediate.
The manganese(V) oxo complex (TBP(8)Cz)Mn(V)(O) (1) is shown to catalyze the epoxidation of alkenes with a series of iodosylarenes (ArIO) as oxidants. Competition experiments reveal that the identity of ArIO influences the product ratios, implicating an unusual coordinated oxo-metal-ArIO intermediate (1-OIAr) as the active catalytic species. The isoelectronic manganese(V) imido complex (TBP(8)Cz)Mn(V)(NMes) (2) does not participate in NR transfer but does catalyze epoxidations with ArIO as the O-atom source, suggesting a mechanism similar to that seen for 1. Direct evidence (ESIMS) is obtained for 1-OIMes.
Leeladee
Pannee
P
Department of Chemistry, Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218, USA.
Goldberg
David P
DP
D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D007094:Imides / Q000737:chemistry*; D008345:Manganese / Q000737:chemistry*; D016877:Oxidants / Q000737:chemistry*; D010084:Oxidation-Reduction
D000475:Alkenes; D007094:Imides; D016877:Oxidants; D008345:Manganese