Conversion of Dinitrogen into Nitrile: Cross‐Metathesis of N₂‐Derived Molybdenum Nitride with Alkynes

Abstract

The direct synthesis of nitrile from N₂ under mild conditions is of great importance and has attracted much interest. Herein, we report a direct conversion of N₂ into nitrile via a nitrile-alkyne cross-metathesis (NACM) process involving a N₂ -derived Mo nitride. Treatment of the Mo nitride with alkyne in the presence of KOTf afforded an alkyne-coordinated nitride, which was then transformed into Mo^V carbyne and the corresponding nitrile upon 1 e^- oxidation. Both aryl- and alkyl-substituted alkynes underwent this process smoothly. Experiments and DFT calculations have proved that the oxidation state of the Mo center plays a crucial role. This method does not rely on the nucleophilicity of the N₂ -derived metal nitride, offering a novel strategy for N₂ fixation chemistry.