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.