Chu Lan-Ye, Ding Yong-Qi, Wang Ming, Ma Jia-Bi
Key Laboratory of Cluster Science of Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 102488, China.
Phys Chem Chem Phys. 2022 Jun 15;24(23):14333-14338. doi: 10.1039/d2cp01817a.
The activation and functionalization of dinitrogen with carbon dioxide into useful chemicals containing C-N bonds are significant research projects but highly challenging. Herein, we report that N molecules are dissociated by heterobimetallic CuNb anions assisted by surface plasma radiation, leading to the formation of CuNbN anions; the CuNbN anions can further react with CO to generate products NCO with one C-N bond and NbONCN with two C-N bonds under thermal collision conditions. For the activation of dinitrogen, the plasma atmosphere is conducive to the dissociation of the NN bond, which renders the coupling reactions of N and CO molecules easier to proceed. This is the first report of coupling of N and CO to generate C-N bonds by making good use of the plasma effect to assist in the activation of N molecules. This new strategy with the assistance of plasma provides a practicable route to construct C-N bonds by directly using N and CO at room temperature.
将氮气与二氧化碳活化并官能团化，转化为含C-N键的有用化学品是重要的研究课题，但极具挑战性。在此，我们报告，在表面等离子体辐射辅助下，异双金属CuNb阴离子使N分子解离，导致形成CuNbN阴离子；在热碰撞条件下，CuNbN阴离子可进一步与CO反应生成含一个C-N键的产物NCO和含两个C-N键的产物NbONCN。对于氮气的活化，等离子体气氛有利于N≡N键的解离，这使得N与CO分子的偶联反应更易进行。这是首次利用等离子体效应辅助活化N分子，实现N与CO偶联生成C-N键的报道。这种等离子体辅助的新策略为在室温下直接利用N和CO构建C-N键提供了一条可行途径。
