Saving the Energy Loss in Lithium-Mediated Nitrogen Fixation by Using a Highly Reactive Li 3 N Intermediate for C-N Coupling Reactions.

Direct synthesis of N-containing organic compounds from dinitrogen (N 2 ) can make synthetic chemistry more sustainable. Previous bottlenecks in lithium-mediated N 2 fixation were resolved by loading Li-metal anodes covered with the typical Li + ion-conducting solid electrolyte interface, which are subsequently allowed to react with N 2 . The developed strategy allowed us to reach high Faradaic efficiencies toward Li 3 N. These reactive Li 3 N were then contacted with acylchlorides. Surface nitride ions are more nucleophilic than amines which direct the two C-N coupling reactions toward formation of imides rather than amides, and an integrated current efficiency of 57-77 % could be realized. This study thereby not only provides a feasible electrochemical Li 3 N synthesis, but also delineates an economical and green synthesis of highly valuable N-containing compounds from N 2 under mild conditions, just using commercial spare parts and processes from the omnipresent Li battery technology.