title: electrochemical generation of a nonheme oxoiron(IV) complex.
abstract: 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.
authors.affiliation: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, USA.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Collins
authors.forename: Kallol
authors.initials: K
authors.lastname: Ray
authors.forename: Lawrence
authors.initials: L
authors.lastname: Que
mesh_terms: D004563:Electrochemistry; D007501:Iron / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D011725:Pyridines / Q000138:chemical synthesis* / Q000737:chemistry; D013053:Spectrophotometry
chemical_list: D009942:Organometallic Compounds; D011725:Pyridines; D007501:Iron