Reaction of CO2 with a Vanadium(II) Aryl Oxide: Synergistic Activation of CO2/Oxo Groups towards H‐Atom Radical Abstraction

Treatment of divalent (ONNO)V(TMEDA) (1; ONNO=[2,4‐Me2‐2‐(OH)C6H2CH2]2N(CH2)2NMe2) with CO2 afforded [(ONNO)V]2(μ‐OH)(μ‐formate) (2). Whereas the bridging hydroxo and formate groups both originated from CO2, the H atoms present on the two residues were obtained through H‐atom radical ion from the solvent. DFT calculations revealed an initially linear CO2 bonding mode, followed by deoxygenation, and highlighted a synergistic effect between the so‐formed oxo group and an additional bridging CO2 residue in promoting radical behavior. Building bridges: A divalent vanadium complex reacted with CO2 to give a complex with bridging hydroxo and formate groups originating from CO2 and containing H atoms ed from the solvent in a radical process. DFT calculations revealed an initially linear CO2 bonding mode, followed by deoxygenation, and highlighted a synergistic effect between the resulting oxo group and an additional bridging CO2 residue in promoting radical H‐atom ion.