Direct Incorporation of Dinitrogen into an Aliphatic C–H Bond

The activation of dinitrogen (N2) 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 Csp3–H bond on the ligand scaffold of a 1,3-propane-bridged [N2N]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 N2 complex and the active nitridyl complex, which is responsible for the Csp3–H amination. This strategy maps an efficient route toward the future synthesis of aliphatic amines directly from N2