Yin Zhu-Bao, Wang Gao-Xiang, Yan Xuechao, Wei Junnian, Xi Zhenfeng
Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing, 100871, China.
Nat Commun. 2025 Jan 15;16(1):674. doi: 10.1038/s41467-025-55998-5.
Direct conversion of dinitrogen (N) into N-containing compounds beyond ammonia under ambient conditions remains a longstanding challenge. Herein, we present a Lewis acid-promoted strategy for diverse nitrogen-element bonds formation from N using chromium dinitrogen complex [Cp*(IPrMe)Cr(N)]K (1). With the help of Lewis acids AlMe and BF, we successfully trap a series of fleeting diazenido intermediates and synthesize value-added compounds containing N-B, N-Ge, and N-P bonds with 3 d metals, offering a method for isolating unstable intermediates. Furthermore, the formation of N-C bonds is realized under more accessible conditions that avoid undesired side reactions. DFT calculations reveal that Lewis acids enhance the participation of dinitrogen units in the frontier orbitals, thereby promoting electrophilic functionalization. Moreover, Lewis acid replacement and a base-induced end-on to side-on switch of [NNMe] unit in [(Cp*(IPrMe)CrNN(BEt)(Me)] (8) are achieved.
在环境条件下将二氮（N₂）直接转化为除氨之外的含氮化合物仍然是一个长期存在的挑战。在此，我们提出了一种由路易斯酸促进的策略，用于使用二氮铬配合物[Cp*(IPrMe)Cr(N₂)]K（1）从N₂形成多种氮元素键。在路易斯酸AlMe₃和BF₃的帮助下，我们成功捕获了一系列瞬态二氮烯基中间体，并与3d金属合成了含有N-B、N-Ge和N-P键的增值化合物，提供了一种分离不稳定中间体的方法。此外，在更易于实现的条件下实现了N-C键的形成，避免了不期望的副反应。密度泛函理论计算表明，路易斯酸增强了二氮单元在前沿轨道中的参与度，从而促进了亲电官能化。此外，还实现了[(Cp*(IPrMe)CrNN(BEt₂)(Me)]（8）中[NNMe]单元的路易斯酸取代以及碱诱导的从端基到侧基的转变。
