Linear and Bridging End‐On coordination modes of CO2 on vanadium(II) and (III) aryloxides

: The second case of linear end-on and evidence for an unprecedented bridging end-on coordination mode of CO2 have been discovered for vanadium aryloxide complexes of the tetradentate ligand system (ONNO)2- (ONNO=2,4-Me2 -2-(OH) C6 H2 CH2 ]2 N(CH2 )2 NMe2 ). The reaction of divalent (ONNO)VII (TMEDA) with CO2 and under the appropriate reaction conditions affords the trivalent (ONNO)VIII (OH)(η1 -CO2 ) resulting from an intermediate CO2 deoxygenation pathway followed by H-atom abstraction from the aromatic solvent, and CO2 fixation. In contrast, the reduction of trivalent (ONNO)VIII Cl(THF) with K, followed by exposure to CO2 in ethereal solvent, afforded the dinuclear [(ONNO)VII ]2 (μ, η1 -CO2 ).