Mutual functionalization of dinitrogen and methane mediated by heteronuclear metal cluster anions CoTaC₂

The direct coupling of dinitrogen (N₂) and methane (CH₄) to construct the N-C bond is a fascinating but challenging approach for the energy-saving synthesis of N-containing organic compounds. Herein we identified a likely reaction pathway for N-C coupling from N₂ and CH₄ mediated by heteronuclear metal cluster anions CoTaC₂ ^-, which starts with the dissociative adsorption of N₂ on CoTaC₂ ^- to generate a Ta -N_t (terminal-nitrogen) Lewis acid-base pair (LABP), followed by the further activation of CH₄ by CoTaC₂N₂ ^- to construct the N-C bond. The N[triple bond, length as m-dash]N cleavage by CoTaC₂ ^- affording two N atoms with strong charge buffering ability plays a key part, which facilitates the H₃C-H cleavage via the LABP mechanism and the N-C formation via a CH₃ migration mechanism. A novel N_t triggering strategy to couple N₂ and CH₄ molecules using metal clusters was accordingly proposed, which provides a new idea for the direct synthesis of N-containing compounds.