Coupling of N₂ and O₂ in the Gas Phase to Synthesize Nitric Oxide at Room Temperature: A Zeldovich-Like Strategy

Dinitrogen (N 2 ) activation and its chemical transformations are some of the most challenging topics in chemistry. Herein, we report that heteronuclear metal anions AuNbBO – can mediate the direct coupling of N 2 and O 2 to generate NO molecules. N 2 first forms the nondissociative adsorption product AuNbBON 2 – on AuNbBO – . In the following reactions with two O 2 molecules, two NO molecules are gradually released, with the formation of AuNbBO 2 N – and AuNbBO 3 – . In the reaction with the first O 2, the generated nitrene radical (N ••– ) originating from the dissociated N 2, induces the activation of O 2 . Subsequently, the second O 2 is anchored and forms a superoxide radical (O 2 •– ); this radical attacks the other N atom to form an N–O bond, releasing the second NO. The N ••– and O 2 •– radicals play key roles in the reactions. The mechanism adopted in this direct oxidation of N 2 by O 2 to NO can be labeled as a Zeldovich-like mechanism.