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

Transition-metal mediated dinitrogen (N₂) splitting into terminal nitrido moiety followed by N-atom transfer is an attractive strategy for N₂ fixation beyond ammonia. While the functionalization of N₂-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 [(^acriPNP)Re(N)Cl] (^acriPNP = 4,5-bis(diisopropylphosphino)-2,7,9,9-tetramethyl-9H-acridin-10-ide) via reductive N₂ 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 N₂ 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 ¹⁵N-labeled nitriles. This work established a two-step synthetic cycle, offering valuable insights into transformations of N₂ into nitrogenous products.