Direct Incorporation of Dinitrogen into an Aliphatic C-H Bond.

The activation of dinitrogen (N 2 ) and direct incorporation of its N atom into C-H bonds to create aliphatic C-N compounds remains unresolved. Incompatible conditions between dinitrogen reduction and C-H functionalization make this process extremely challenging. Herein, we report the first example of dinitrogen insertion into an aliphatic C sp 3 -H bond on the ligand scaffold of a 1,3-propane-bridged [N 2 N] 2- -type dititanium complex. Mechanistic investigations on the behaviors of dinuclear and mononuclear Ti complexes indicated the intramolecular synergistic effect of two Ti centers at a C-N bond-forming step. Computational studies revealed the critical isomerization between the inactive side-on N 2 complex and the active nitridyl complex, which is responsible for the C sp 3 -H amination. This strategy maps an efficient route toward the future synthesis of aliphatic amines directly from N 2 .