DFT Mechanistic Account for the Site Selectivity of Electron-Rich C(sp<sup>3</sup>)–H Bond in the Manganese-Catalyzed Aminations
Zheyuan Liu, Yu Lu, Jiandong Guo, Wenping Hu, Yanfeng Dang, Zhixiang Wang
Abstract
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.
Topics & Concepts
ChemistryManganeseAminationCatalysisElectron transferBond cleavageHydrideDissociation (chemistry)Hydrogen atomRedoxSelectivityLigand (biochemistry)PhotochemistryHydrogenInorganic chemistryOrganic chemistryAlkylBiochemistryReceptorSynthesis and Catalytic ReactionsCatalytic C–H Functionalization MethodsMetal-Catalyzed Oxygenation Mechanisms