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.