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

The direct synthesis of nitrile from N under mild conditions is of great importance and has attracted much interest. Herein, we report a direct conversion of N into nitrile via a nitrile-alkyne cross-metathesis (NACM) process involving a N -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 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 N -derived metal nitride, offering a novel strategy for N fixation chemistry.