Upside Down! Crystallographic and Spectroscopic Characterization of an [FeIV(Osyn)(TMC)]2+ Complex

Abstract

FeII(TMC)(OTf)2 reacts with 2-tBuSO2-C6H4IO to afford an oxoiron(IV) product, 2, distinct from the previously reported [FeIV(Oanti)(TMC)(NCMe)]2+. In MeCN, 2 has a blue-shifted near-IR band, a higher ν(Feî - ?O), a larger Mössbauer quadrupole splitting, and quite a distinct 1H NMR spectrum. Structural analysis of crystals grown from CH2Cl2 reveals a complex with the formulation of [FeIV(Osyn)(TMC)(OTf)](OTf) and the shortest FeIVî - ?O bond [1.625(4) Å] found to date.