Sc3+-triggered oxoiron(IV) formation from O2 and its non-heme iron(II) precursor via a Sc3+-peroxo-Fe3+ intermediate

Article abstract of DOI:10.1021/ja402645y

We report that redox-inactive Sc³⁺ can trigger O₂ activation by the Fe^II(TMC) center (TMC = tetramethylcyclam) to generate the corresponding oxoiron(IV) complex in the presence of BPh ₄^- as an electron donor. To model a possible intermediate in the above reaction, we generated an unprecedented Sc³⁺ adduct of [Fe^III(η²-O₂)(TMC)]⁺ by an alternative route, which was found to have an Fe³⁺-(μ- η²:η²-peroxo)-Sc³⁺ core and to convert to the oxoiron(IV) complex. These results have important implications for the role a Lewis acid can play in facilitating O-O bond cleavage during the course of O₂ activation at non-heme iron centers.