Mou Li-Hui, Li Yao, Wei Gong-Ping, Li Zi-Yu, Liu Qing-Yu, Chen Hui, He Sheng-Gui
State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences Beijing 100190 P. R. China
Beijing National Laboratory for Molecular Sciences and CAS Research/Education Center of Excellence in Molecular Sciences Beijing 100190 P. R. China.
Chem Sci. 2022 Jul 14;13(32):9366-9372. doi: 10.1039/d2sc02416k. eCollection 2022 Aug 17.
The direct coupling of dinitrogen (N) and methane (CH) 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 and CH mediated by heteronuclear metal cluster anions CoTaC , which starts with the dissociative adsorption of N on CoTaC to generate a Ta -N (terminal-nitrogen) Lewis acid-base pair (LABP), followed by the further activation of CH by CoTaCN to construct the N-C bond. The N[triple bond, length as m-dash]N cleavage by CoTaC affording two N atoms with strong charge buffering ability plays a key part, which facilitates the HC-H cleavage the LABP mechanism and the N-C formation a CH migration mechanism. A novel N triggering strategy to couple N and CH molecules using metal clusters was accordingly proposed, which provides a new idea for the direct synthesis of N-containing compounds.
将氮气（N₂）和甲烷（CH₄）直接偶联以构建N-C键，是一种用于含氮有机化合物节能合成的引人入胜但具有挑战性的方法。在此，我们确定了由异核金属簇阴离子CoTaC₆介导的N₂和CH₄之间N-C偶联的可能反应途径，该途径始于N₂在CoTaC₆上的解离吸附，生成Ta-N（端基氮）路易斯酸碱对（LABP），随后CoTaCN₆进一步活化CH₄以构建N-C键。CoTaC₆对N≡N的裂解产生了具有强电荷缓冲能力的两个N原子，这起到了关键作用，它促进了通过LABP机制的HC-H裂解以及通过CH迁移机制的N-C形成。据此提出了一种使用金属簇偶联N₂和CH₄分子的新型N₂触发策略，为含氮化合物的直接合成提供了新思路。
