electrochemical generation of a nonheme oxoiron(IV) complex

The complex Fe(IV)O(N4Py)]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) has been prepared by bulk electrolysis in aqueous CH3CN and CH2Cl2, and its redox properties characterized. Bulk chronocoulometry and spectropotentiometry experiments in CH3CN show that Fe(II)(N4Py)(NCCH3)]2+ can be oxidized quantitatively to its iron(III) derivative at an applied potential of +0.71 V vs ferrocene and then to the oxoiron(IV) complex (in the presence of added water) at potentials above +1.3 V. The E1/2 value for the Fe(IV/III) couple has been estimated to be +0.90 V from spectropotentiometric titrations in CH3CN and cyclic voltammetric measurements in CH2Cl2.