Plasma-promoted reactions of the heterobimetallic anions CuNb⁻ with dinitrogen and subsequent reactions with carbon dioxide: formation of C-N bonds

The activation and functionalization of dinitrogen with carbon dioxide into useful chemicals containing C-N bonds are significant research projects but highly challenging. Herein, we report that N₂ molecules are dissociated by heterobimetallic CuNb⁻ anions assisted by surface plasma radiation, leading to the formation of CuNbN₂⁻ anions; the CuNbN₂⁻ anions can further react with CO₂ to generate products NCO⁻ with one C-N bond and NbO₂NCN⁻ with two C-N bonds under thermal collision conditions. For the activation of dinitrogen, the plasma atmosphere is conducive to the dissociation of the N ≡ N bond, which renders the coupling reactions of N₂ and CO₂ molecules easier to proceed. This is the first report of coupling of N₂ and CO₂ to generate C-N bonds by making good use of the plasma effect to assist in the activation of N₂ molecules. This new strategy with the assistance of plasma provides a practicable route to construct C-N bonds by directly using N₂ and CO₂ at room temperature.