Tuning the H‐Atom Transfer Reactivity of Iron(IV)‐Oxo Complexes as Probed by Infrared Photodissociation Spectroscopy

Reactivities of non‐heme iron(IV)‐oxo complexes are mostly controlled by the ligands. Complexes with tetradentate ligands such as [(TPA)FeO](2+) (TPA=tris(2‐pyridylmethyl)amine) belong to the most reactive ones. Here, we show a fine‐tuning of the reactivity of [(TPA)FeO](2+) by an additional ligand X (X=CH(3)CN, CF(3)SO(3) (−), ArI, and ArIO; ArI=2‐((t)BuSO(2))C(6)H(4)I) attached in solution and reveal a thus far unknown role of the ArIO oxidant. The HAT reactivity of [(TPA)FeO(X)](+/2+) decreases in the order of X: ArIO > MeCN > ArI ≈ TfO(−). Hence, ArIO is not just a mere oxidant of the iron(II) complex, but it can also increase the reactivity of the iron(IV)‐oxo complex as a labile ligand. The detected HAT reactivities of the [(TPA)FeO(X)](+/2+) complexes correlate with the Fe=O and FeO−H stretching vibrations of the reactants and the respective products as determined by infrared photodissociation spectroscopy. Hence, the most reactive [(TPA)FeO(ArIO)](2+) adduct in the series has the weakest Fe=O bond and forms the strongest FeO−H bond in the HAT reaction.