Synthesis of Nitriles from Dinitrogen via N‐Atom Transfer on Rhenium Nitride Complex

Abstract Transition‐metal mediated dinitrogen (N 2 ) splitting into terminal nitrido moiety followed by N‐atom transfer is an attractive strategy for N 2 fixation beyond ammonia. While the functionalization of N 2 ‐derived nitride complexes have been widely investigated, their N‐atom transfer reactions to provide N‐containing organic compounds were rarely reported. Herein, we report the synthesis of a rhenium nitride complex [( acri PNP)Re(N)Cl] ( acri PNP = 4,5‐bis(diisopropylphosphino)‐2,7,9,9‐tetramethyl‐9H‐acridin‐10‐ide) via reductive N 2 cleavage from either rhenium trichloride or rhenium oxo dichloride complexes. The rhenium nitride exhibits N‐atom transfer reactivity with acyl triflates or chlorides under mild conditions, affording nitriles concomitant with the regeneration of the nitride precursors, rhenium oxo or trichloride complexes, respectively. This overall N‐atom transfer from N 2 to acyl electrophiles produced a series of alkyl, aryl, and heterocyclic nitriles, in moderate to good yields, offering a versatile and practical strategy for accessing 15 N‐labeled nitriles. This work established a two‐step synthetic cycle, offering valuable insights into transformations of N 2 into nitrogenous products.