Hydrocarbon Oxidation by an Exposed, Multiply Bonded Iron(III) Oxo Complex

The iron oxo unit, [FeO] n+ is a critical intermediate in biological oxidation reactions. While its higher oxidation states are well studied, relatively little is known about the least-oxidized form [FeIIIO]+. Here, the thermally stable complex PhB­(AdIm)3FeO has been structurally, spectroscopically, and computationally characterized as a bona fide iron­(III) oxo. An unusually short Fe–O bond length is consistent with iron–oxygen multiple bond character and is supported by electronic structure calculations. The complex is thermally stable yet is able to perform hydrocarbon oxidations, facilitating both C–O bond formation and dehydrogenation reactions.