Mutual functionalization of dinitrogen and methane mediated by heteronuclear metal cluster anions CoTaC 2 .

The direct coupling of dinitrogen (N 2 ) and methane (CH 4 ) 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 N 2 and CH 4 mediated by heteronuclear metal cluster anions CoTaC 2 - , which starts with the dissociative adsorption of N 2 on CoTaC 2 - to generate a Ta δ + -N t δ - (terminal-nitrogen) Lewis acid-base pair (LABP), followed by the further activation of CH 4 by CoTaC 2 N 2 - to construct the N-C bond. The N[triple bond, length as m-dash]N cleavage by CoTaC 2 - affording two N atoms with strong charge buffering ability plays a key part, which facilitates the H 3 C-H cleavage via the LABP mechanism and the N-C formation via a CH 3 migration mechanism. A novel N t triggering strategy to couple N 2 and CH 4 molecules using metal clusters was accordingly proposed, which provides a new idea for the direct synthesis of N-containing compounds.