Redox-Active Ligands Permit Multielectron O₂ Homolysis and O-Atom Transfer at Exceptionally High-Valent Vanadyl Complexes.

ABSTRACT: A five-coordinate chlorovanadium species supported by two redox-active N-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

SUBMITTER: Hill AG 

PROVIDER: S-EPMC12023041 | biostudies-literature | 2025 Apr

REPOSITORIES: biostudies-literature