Coupling of N 2 and O 2 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.