Determining the Inherent Selectivity for Carbon Radical Hydroxylation versus Halogenation with Fe<sup>III</sup>(OH)(X) Complexes: Relevance to the Rebound Step in Non-heme Iron Halogenases
Vishal Yadav, Rodolfo J. Rodriguez, Maxime A. Siegler, David P. Goldberg
Abstract
The first structural models of the proposed cis-FeIII(OH)(halide) intermediate in the non-heme iron halogenases were synthesized and examined for their inherent reactivity with tertiary carbon radicals. Selective hydroxylation occurs for these cis-FeIII(OH)(X) (X = Cl, Br) complexes in a radical rebound-like process. In contrast, a cis-FeIII(Cl)2 complex reacts with carbon radicals to give halogenation. These results are discussed in terms of the inherent reactivity of the analogous rebound intermediate in both enzymes and related catalysts.
Topics & Concepts
ChemistryReactivity (psychology)HydroxylationHalogenationRadicalSelectivityMedicinal chemistryHalideCarbon fibersHemeCatalysisStereochemistryPhotochemistryOrganic chemistryEnzymeComposite materialMedicineAlternative medicineMaterials sciencePathologyComposite numberMetal-Catalyzed Oxygenation MechanismsVanadium and Halogenation ChemistryCO2 Reduction Techniques and Catalysts