Reaction of Metal Anionic Centers with Carbon Dioxide: The Case of V^- + CO₂

Wave function and density functional theory calculations are employed to investigate the reaction of V^- with CO₂ for the ground and low-lying excited asymptotic channels. Our calculated potential energy profiles suggest that an electron transfer occurs from the 4s orbital of vanadium to carbon dioxide when CO₂ approaches V^- at about 3 Å. This process enables the formation of a covalent bond between V and ${\mathrm{CO}}_2^{-}$ in a way that is almost barrier-free. At equilibrium $\left({\mathrm{VCO}}_2^{-}\right)$, the CO₂ moiety makes a side-on bond with the metal center, and after a barrier of about 10 kcal/mol, it can lead to the cleavage of the coordinated CO bond. The formed OVCO^- can readily release CO, while the remaining VO^- can be used as an oxidizing agent, paving the way for the utilization of CO₂ as an oxidant. Our study highlights the potential of metal anionic centers to efficiently capture and exploit CO₂ sources with a view to addressing both energy-relevant and atmospheric-important concerns. Future studies can further reveal the potential of using metal anionic centers to incorporate CO₂ into organic molecules.