Direct Amination of Benzene with Molecular Nitrogen Enabled by Plasma‐Liquid Interactions

Abstract Nitrogen fixation is industrially realized by mass production of ammonia, the principal intermediate nitrogen source for N‐containing organic molecules. Instead, direct C−N bond formation from dinitrogen (N2) is of great interest but remains a challenge. Here, by virtue of unique plasma–liquid interactions, we developed an environmentally benign one‐pot approach to directly couple benzene and N2, two naturally abundant yet chemically inert molecules, into value‐added arylamines. Under the optimal conditions, an amination yield of 45 % was rapidly achieved, far better than the reported benzene amination efficiency using ammonia. A tentative reaction mechanism was proposed involving the long‐lived N2 (A3 ) and N2+ species, as evidenced by the key intermediates detected. With a deeper mechanistic understanding and by further optimizing the plasma reactor, the realization of cost‐effective electrical amination of benzene with N2 could become reality.