Inorganic Chemistry · 2010 · 56 citations · 0 references
Natural SciencesChemistryCatalysisInorganic ChemistryRedox BiochemistryCatalytic MechanismsMetal CatalysisMetal Ion CatalysisMetal OxidesRedox CatalysisManganese CatalysisManganese ChemistryManganese Oxide CatalystsManganese Redox ChemistryMetal Oxide CatalysisMetal Oxide CatalystsMetal-catalyzed OxidationMetal-oxo Complexes
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.