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

Research paper by Jai Prakash, Gregory T. Rohde, Katlyn K. Meier, Eckard Münck, Lawrence Que

Indexed on: 25 Nov '15Published on: 24 Nov '15Published in: Inorganic Chemistry



Abstract

FeII(TMC)(OTf)2 reacts with 2-tBuSO2−C6H4IO to afford an oxoiron(IV) product distinct from the previously reported [FeIV(Oanti)(TMC)(NCMe)]2+, as indicated by its different spectroscopic features. X-ray crystallography shows that the new complex has its O atom occupying the syn face of the TMC ligand and reveals the shortest FeIV═O bond [1.625(4) Å] found to date.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(Fe═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 FeIV═O bond [1.625(4) Å] found to date.

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