Plasma-Assisted Coupling Reactions of Dinitrogen and Carbon Dioxide Mediated by Monometallic YB_1–4⁻⋅Anions: Carbon−Nitrogen Bond Formation

Transition-metal catalyzed coupling to form C−N bonds is significant in chemical science. However, the inert nature of N₂ and CO₂ renders their coupling quite challenging. Herein, we report the activation of dinitrogen in the mild plasma atmosphere by the gas-phase monometallic YB_1–4⁻ anions and further coupling of CO₂ to form C−N bonds by using mass spectrometry and theoretical calculation. The observed product anions are NCNBO⁻ and N(BO)₂⁻, accompanied by the formation of neutral products YO and YB_0–2NC, respectively. We can tune the reactivity and the type of products by manipulating the number of B atoms. The B atoms in YB_1–4N₂⁻ act as electron donors in CO₂ reduction reactions, and the carbon atom originating from CO₂ serves as an electron reservoir. This is the first example of gas-phase monometallic anions, which are capable to realize the functionalization of N₂ with CO₂ through C−N bond formation and N−N and C−O bond cleavage.