论文部分内容阅读
The oxidation of various alkanes catalyzed by [MnⅤ(N)(CN)4]2-using various terminal oxidants at room temperature has been investigated.Excellent yields of alcohols and ketones (＞95％) are obtained using H2O2 as oxidant and CF3CH2OH as solvent.Good yields (＞80％) are also obtained using (NH4)2[Ce(NO3)6] in CF3CH2OH/H2O.Based on the experimental results, the proposed mechanism for catalytic alkane oxidation by [MnⅤ(N)(CN)4]2-/ROOH involves initial rate-limiting O-atom transfer from ROOH to [Mn(N)(CN)4]2-to generate a manganese(Ⅶ) nitrido oxo active species, [MnⅦ(N)(O)(CN)4]2-, which then oxidizes alkanes (RH) via a H-atom abstraction/O-rebound mechanism.