Structural Insights into Nonheme Alkylperoxoiron(III) and Oxoiron(IV) Intermediates by X-ray Absorption Spectroscopy

Transient mononuclear low-spin alkylperoxoiron(III) and oxoiron(IV) complexes that are relevant to the activation of dioxygen by nonheme iron enzymes have been generated from synthetic iron(II) complexes of neutral tetradentate (TPA) and pentadentate (N4Py, Bn-TPEN) ligands and structurally characterized by means of Fe K-edge X-ray absorption spectroscopy (XAS). Notable features obtained from fits of the EXAFS region are Fe−O bond lengths of 1.78 Å for the alkylperoxoiron(III) intermediates and 1.65−1.68 Å for the oxoiron(IV) intermediates, reflecting different strengths in the Fe−O π interactions. These differences are also observed in the intensities of the 1s-to-3d transitions in the XANES region, which increase from 4 units for the nearly octahedral iron(II) precursor to 9−15 units for the alkylperoxoiron(III) intermediates to 25−29 units for the oxoiron(IV) species.