近日，湖南大学邹雨芹团队报道了近化学计量电催化C-N偶联的金属缺陷对。这一研究成果于2026年4月9日发表在《国家科学评论》杂志上。

传统上，交叉偶联反应允许在过渡金属催化下，于芳基亲核试剂与芳基亲电试剂之间形成Ar-Ar键。迄今为止，众多已知的交叉偶联反应之所以具有高选择性，依赖于亲核和亲电偶联配偶体的特定组合，其机理基础在于亲核试剂与亲电试剂经历根本不同的催化步骤，从而在反应性上得以区分。

研究组报道了一类双亲性芳基铋试剂，它们在过渡金属催化的交叉偶联反应中可以表现为亲核试剂或亲电试剂，从根本上打破了这种反应性上的二分法。化学计量反应和机理研究表明，这种双亲反应性源于它们能够同时参与与过渡金属配合物的氧化加成和金属交换过程。通过证明单一的芳基试剂能够参与这两个经典的基本步骤，该研究挑战了长期以来的假设，即固有的键极性严格决定了交叉偶联化学中的机理角色。

附：英文原文

Title: Metal-defect pairs for near-stoichiometric electrocatalytic C–N coupling

Author: Wu, Yandong, Chen, Wei, Zou, Yuqin, Wang, Jinbo, Wang, Ruiqi, Hu, Nan, Liu, Qie, Qiu, Mengyi, Huang, Yu-Cheng, Jiang, Yimin, Han, Mengwei, Yang, Ming, Xu, Leitao, Chen, Jiawang, Xie, Chao, Wang, Dongdong, Xu, Yabin, Lu, Ying-Rui, He, Yongmin, Li, Xuning, Fan, Liwu, Gao, Xiang, Wang, Shuangyin

Issue&Volume: 2026-04-09

Abstract: Geminal-site catalysts (GSCs) are prospective candidates to fulfill the goal of aqueous electrochemical reductive cross-coupling reactions (ERCR) at near-stoichiometric yields. Nevertheless, the problem lies in lacking the synthetic route of GSCs with few single sites. Here we report a defect-accompanying strategy for synthesizing GSCs containing metal-defect catalytic pairs (M-D GSCs), and thereinto, Fe-D GSCs can realize the electrochemical synthesis of cyclohexanone oximes (CHO) from high concentrations (0.5 M) of nitrites (NO2) and cyclohexanone (CYC) at near-stoichiometric yields (the Faradic efficiency or yieldC/N: 91.3%). Multiple in/ex-situ characterizations demonstrated that metal-citrate complexes were converted to metal-defect catalytic pairs via the liberation of gaseous carbon/nitrogen species during pyrolysis. Furthermore, we developed an innovative cathodic oxime-alkali process, where high concentration NaNO2 and CYC can be electrochemically converted to high purity products including NaOH and CHO. This work showcases the enormous potential of M-D GSCs in achieving near-stoichiometric conversion for ERCR reactions.

DOI: 10.1093/nsr/nwag206

Source: https://dx.doi.org/10.1093/nsr/nwag206