Synthesis of Nitriles from Dinitrogen via N-Atom Transfer on Rhenium Nitride Complex
Chunxiao Shan, Yue Wu, Zhu-Bao Yin, Junnian Wei*, Zhenfeng Xi*
Angew. Chem. Int. Ed. 2025. DOI: 10.1002/anie.202506857.
Transition-metal mediated dinitrogen (N2) splitting intoterminal nitrido moiety followed by N-atom transfer is an attractivestrategy for N2 fixation beyond ammonia. While the functionalizationof N2-derived nitride complex has been widely investigated, their N-atom transfer reactions to provide N-containing organic compoundswere rarely reported. Herein, we report the synthesis of a rheniumnitride complex [(acriPNP)Re(N)Cl] (acriPNP = 4,5-bis(diisopropylphosphino)-2,7,9,9-tetramethyl-9H-acridin-10-ide) viareductive N2 cleavage from either rhenium trichloride or rhenium oxodichloride complexes. The rhenium nitride exhibits N-atom transferreactivity with acyl triflates or chlorides under mild conditions,affording nitriles concomitant with the regeneration of the nitrideprecursors, rhenium oxo or trichloride complexes, respectively. Thisoverall N-atom transfer from N2 to acyl electrophiles produced aseries alkyl, aryl, and heterocyclic nitriles, in moderate to good yields,offering a versatile and practical strategy for accessing 15N-labelednitriles. This work established a two-step synthetic cycle, offeringvaluable insights into transformations of N2 into nitrogenous products.
