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Structural modeling of iron halogenases: synthesis and reactivity of halide-iron(IV)-oxo compounds
Oriol Planas1, Martin Clémancey, Jean-Marc Latour
1Grup de Química Bioinorgànica i Supramolecular (QBIS), Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, E17071 Girona, Catalonia, Spain. anna.company@udg.edu miquel.costas@udg.edu.
Abstract:
A structural synthetic model of the iron(IV)-oxo-halide active species of non-heme iron dependent halogenases is reported. Compounds with general formula [Fe(IV)(O)(X)(Pytacn)](+) (1-X, X = Cl, Br) have been prepared and characterized spectroscopically and chemically with regard to their oxidizing ability. 1-X performs hydrogen-atom abstraction of C-H bonds at reaction rates 2-3 times faster than the corresponding solvato dicationic species, thus modelling the first step in C-H functionalization taking place in natural halogenation.
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