Dinitrogen and Carbon Dioxide Activation to Form C–N Bonds at Room Temperature: A New Mechanism Revealed by Experimental and Theoretical Studies

Abstract

In light of the current energy requirements, the conversion of CO₂ and N₂ into useful C-N bond-containing products under mild conditions has become an area of intense research. However, the inert nature of N₂ and CO₂ renders their coupling extremely challenging. Herein, nitrogen and carbon atoms originating from N₂ and CO₂, respectively, are fixed sequentially by NbH₂^- anions in the gas phase at room temperature. Isocyanate and NbO₂CN^- anions were formed under thermal collision conditions, thus achieving the formation of new C-N bonds directly from simple N₂ and CO₂. The anion structures and reaction details were studied by mass spectrometry, photoelectron spectroscopy, and quantum chemical calculations. A novel N₂ activation mode (metal-ligand activation, MLA) and a related mechanism for constructing C-N bonds mediated by a single non-noble metal atom are proposed. In this MLA mode, the C atom originating from CO₂ serves as an electron reservoir to accept and donate electrons.