Structural modeling of iron halogenases: synthesis and reactivity of halide-iron(Ⅳ)-oxo compounds

摘要

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.