Construction of N−E bonds via Lewis acid-promoted functionalization of chromium-dinitrogen complexes

Direct conversion of dinitrogen (N2) 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 N2 using chromium dinitrogen complex [Cp*(IiPr2Me2)Cr(N2)2]K (1). With the help of Lewis acids AlMe3 and BF3, we successfully trapped a series of fleeting diazenido intermediates and synthesized value-added compounds containing N−B, N−Ge, and N−P bonds with 3d metals for the first time, offering a new method for isolating unstable intermediates. Furthermore, the formation of N−C bonds was realized under more accessible conditions that avoided undesired side reactions. DFT calculations revealed that Lewis acids enhanced the participation of dinitrogen units in the frontier orbitals, thereby promoting electrophilic functionalization.