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

Dinitrogen (N2) 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 N2 and O2 to generate NO molecules. N2 first forms the nondissociative adsorption product AuNbBON2- on AuNbBO-. In the following reactions with two O2 molecules, two NO molecules are gradually released, with the formation of AuNbBO2N- and AuNbBO3-. In the reaction with the first O2, the generated nitrene radical (N••-) originating from the dissociated N2, induces the activation of O2. Subsequently, the second O2 is anchored and forms a superoxide radical (O2•-); this radical attacks the other N atom to form an N-O bond, releasing the second NO. The N••- and O2•- radicals play key roles in the reactions. The mechanism adopted in this direct oxidation of N2 by O2 to NO can be labeled as a Zeldovich-like mechanism.