Plasma-Assisted Coupling Reactions of Dinitrogen and Carbon Dioxide Mediated by Monometallic YB ⋅Anions: Carbon-Nitrogen Bond Formation.

Transition-metal catalyzed coupling to form C-N bonds is significant in chemical science. However, the inert nature of N and CO renders their coupling quite challenging. Herein, we report the activation of dinitrogen in the mild plasma atmosphere by the gas-phase monometallic YB anions and further coupling of CO to form C-N bonds by using mass spectrometry and theoretical calculation. The observed product anions are NCNBO and N(BO) , accompanied by the formation of neutral products YO and YB NC, respectively. We can tune the reactivity and the type of products by manipulating the number of B atoms. The B atoms in YB N act as electron donors in CO reduction reactions, and the carbon atom originating from CO serves as an electron reservoir. This is the first example of gas-phase monometallic anions, which are capable to realize the functionalization of N with CO through C-N bond formation and N-N and C-O bond cleavage.