In the first step, the reactive intermediate complex (IM) is formed by abstracting the hydrogen at the cost of a moderate energy barrier of 17.7 kcal/mol, which is lowered to 12.3 kcal/mol using the more extensive basis set. This less exothermic step is rate-determining. Subsequently, IM proceeds through the radical rebound mechanism that possesses a tiny energy barrier of 2.5 kcal/mol and forms the C-H aminated product. The optimized geometry of TS1 can be found in the SI.