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Oxoiron(V) species are postulated to be involved in the mechanisms of the arenecis -dihydroxylating Rieske dioxygenases and of bioinspired nonheme iron catalysts for alkane hydroxylation, olefincis -dihydroxylation, and water oxidation. In an effort to obtain a synthetic oxoiron(V) complex, we report herein the one-electron oxidation of theS  = 1 complex [FeIV (O)(TMC)(NCCH3 )]2+ (1 , where TMC is tetramethylcyclam) by treatment withtert -butyl hydroperoxide and strong base in acetonitrile to generate a metastablecomplex2 at -44 °C, which has been characterized by UV-visible, resonance Raman, Mössbauer, and EPR methods. The defining spectroscopic characteristic of2 is the unusualx /y anisotropy observed for the57 Fe and17 O A tensors associated with the high-valent Fe═O unit and for the14 N A tensor of a ligand derived from acetonitrile. As shown by detailed density functional theory (DFT) calculations, the unusualx /y anisotropy observed can only arise from an iron center with substantially different spin populations in the dxz and dyz orbitals, which cannot correspond to an FeIV ═O unit but is fully consistent with anFeV center, like that found for [FeV (O)(TAML)]- (where TAML is tetraamido macrocyclic ligand), the only well-characterized oxoiron(V) complex reported. Mass spectral analysis shows that the generation of2 entails the addition of an oxygen atom to1 and the loss of one positive charge. Taken together, the spectroscopic data and DFT calculations support the formulation of2 as an iron(V) complex having axial oxo and acetylimido ligands, namely [FeV (O)(TMC)(NC(O)CH3 )]+ .

One-electron oxidation of an oxoiron(IV) complex to form an [O═Fe V ═NR] + center

One-electron oxidation of an oxoiron(IV) complex to form an [O═Fe ^V ═NR] ⁺ center