Litcius/Paper detail

Conversion of Dinitrogen into Nitrile: Cross‐Metathesis of N<sub>2</sub>‐Derived Molybdenum Nitride with Alkynes

Jinyi Song, Qian Liao, Xin Hong, Li Jin, Nicolas Mézailles

2021Angewandte Chemie International Edition61 citationsDOIOpen Access PDF

Abstract

Abstract The direct synthesis of nitrile from N 2 under mild conditions is of great importance and has attracted much interest. Herein, we report a direct conversion of N 2 into nitrile via a nitrile–alkyne cross‐metathesis (NACM) process involving a N 2 ‐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 N 2 ‐derived metal nitride, offering a novel strategy for N 2 fixation chemistry.

Topics & Concepts

NitrileAlkyneMolybdenumNitrideNucleophileCarbyneMetathesisChemistryArylCombinatorial chemistryAlkylPhotochemistryOrganic chemistryCarbeneCatalysisPolymerPolymerizationLayer (electronics)MXene and MAX Phase MaterialsAmmonia Synthesis and Nitrogen ReductionSynthetic Organic Chemistry Methods