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 CO2- in a way that is almost barrier-free. At equilibrium (VCO2-), 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.