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

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 MoV 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.