Reaction of Metal Anionic Centers with Carbon Dioxide: The Case of V ^– + CO ₂

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 <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msubsup><mml:mrow><mml:mi>CO</mml:mi></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow><mml:mrow><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:math> in a way that is almost barrier-free. At equilibrium <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mo>(</mml:mo><mml:msubsup><mml:mrow><mml:mi>VCO</mml:mi></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow><mml:mrow><mml:mo>-</mml:mo></mml:mrow></mml:msubsup><mml:mo>)</mml:mo></mml:math>, 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.