DFT Mechanistic Account for the Site Selectivity of Electron-Rich C(sp3)-H Bond in the Manganese-Catalyzed Aminations.

DFT study suggests that the C-H cleavage involved in the C(sp3)-H amination catalyzed by manganese perchlorophthalocyanine complex [MnIII(ClPc)]+ proceeds via hydride transfer (HYT), instead of hydrogen atom transfer (HAT), thus elucidating why the reaction favors aminating the electron-rich C-H bond, rather than that with smaller bond dissociation energy preferred by HAT. Detailed analyses indicate the HYT actually occurs via concerted electron and hydrogen atom transfers and the redox-active ClPc ligand enables the HYT.