Xihua Wang, Yong Wang, Pengsong Li, Xiang‐Da Zhang, Congyang Wang, Mingfei Shao, Yuqing Hou, Ganwen Zhang, Huizhen Liu, X. L. Kang, Qingli Qian, Lihong Jing, Qinggong Zhu, Buxing Han
This spin arrangement creates a spin relay active center that promotes spin-matched C–N coupling between *N(CH 3 ) 2 and *CHO intermediates, lowing the reaction energy barrier.
Formamides are indispensable building blocks in pharmaceuticals and fine chemicals, yet their sustainable synthesis remains challenging. Herein, we present the first electrochemical strategy for the direct synthesis of N, N -dimethylformamide (DMF) via dimethylamine (DMA) self-coupling, eliminating the need of external carbon sources. The designed Cr 2 WO 6 catalyst features a Cr–W–Cr motif, where the Cr sites can exhibit either positive and negative spin moments. This spin arrangement creates a spin relay active center that promotes spin-matched C–N coupling between *N(CH 3 ) 2 and *CHO intermediates, lowing the reaction energy barrier. Notably, with a DMA concentration of 0.1 M, the system delivers a DMF Faradaic efficiency of 45.0% and a yield rate of 21.3 μmol cm –2 h –1 . At 0.5 M DMA, the yield rate further increases to 60.0 μmol cm –2 h –1 . This work opens a sustainable and efficient route for DMF production and highlights spin alignment as a design principle for electrochemical C–N bond formation.