Radical Behavior of CO2 versus its Deoxygenation Promoted by Vanadium Aryloxide Complexes: How the Geometry of Intermediate CO2 -Adducts Determines the Reactivity.

The reactivity of carbon dioxide with vanadium(III) aryloxo complexes has been investigated. The formation of either carbon monoxide or incorporation into the ligand system with the ultimate formation of organic ester was observed depending on the overall electron donor ability of the ligand field. DFT calculations were carried out to investigate the proposed mechanism for carbon dioxide coordination and reduction.