biostudies-literatureHill AGAmerican Chemical Society Petroleum Research FundGeorgia Institute of Technology13356-13369https://www.ebi.ac.uk/biostudies/studies/S-EPMC12023041biostudies-literatureUnknown147(16)A five-coordinate chlorovanadium species supported by two redox-active <i>N</i>-phenyl aminophenol ligands was prepared. Experimental and computational data support formulation of this complex as [(^Phap)(^Phisq)V^IVCl], containing one dianionic [^Phap]^2- amidophenolate and one monoanionic [^Phisq]^•- iminosemiquinonate radical. Exposure of [(^Phap)(^Phisq)V^IVCl] to O₂ readily cleaves the O═O bond to generate [(^Phisq)(^Phibq)V^IV(O)Cl], containing an [^Phibq] iminobenzoquinone, so the 2e^- oxidation is entirely ligand centered. [(^Phisq)(^Phibq)V^IV(O)Cl] is reduced by net H₂ abstraction Journal of the American Chemical SocietyRedox-Active Ligands Permit Multielectron O&lt;sub&gt;2&lt;/sub&gt; Homolysis and O-Atom Transfer at Exceptionally High-Valent Vanadyl Complexes.PMC1202304165353-ND3Partnership for an Advanced Computing EnvironmentCastillo MCHill AGBacsa JOtte KSSoper JDfalseRedox-Active Ligands Permit Multielectron O&lt;sub&gt;2&lt;/sub&gt; Homolysis and O-Atom Transfer at Exceptionally High-Valent Vanadyl Complexes.A five-coordinate chlorovanadium species supported by two redox-active <i>N</i>-phenyl aminophenol ligands was prepared. Experimental and computational data support formulation of this complex as [(^Phap)(^Phisq)V^IVCl], containing one dianionic [^Phap]^2- amidophenolate and one monoanionic [^Phisq]^•- iminosemiquinonate radical. Exposure of [(^Phap)(^Phisq)V^IVCl] to O₂ readily cleaves the O═O bond to generate [(^Phisq)(^Phibq)V^IV(O)Cl], containing an [^Phibq] iminobenzoquinone, so the 2e^- oxidation is entirely ligand centered. [(^Phisq)(^Phibq)V^IV(O)Cl] is reduced by net H₂ abstraction 2025-01-01T00:00:00Z2025 Apr2025-06-26T03:05:45.505Z2025-06-26T03:05:45.505ZS-EPMC120230414020060110.1021/jacs.4c18305