title: Crystallographic and spectroscopic characterization of a nonheme Fe(IV)-O complex.
abstract: Following the heme paradigm, it is often proposed that dioxygen activation by nonheme monoiron enzymes involves an iron(IV)=oxo intermediate that is responsible for the substrate oxidation step. Such a transient species has now been obtained from a synthetic complex with a nonheme macrocyclic ligand and characterized spectroscopically. Its high-resolution crystal structure reveals an iron-oxygen bond length of 1.646(3) angstroms, demonstrating that a terminal iron(IV)=oxo unit can exist in a nonporphyrin ligand environment and lending credence to proposed mechanisms of nonheme iron catalysis.
authors.affiliation: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455, USA.
authors.forename: Jan-Uwe
authors.initials: JU
authors.lastname: Rohde
authors.forename: Jun-Hee
authors.initials: JH
authors.lastname: In
authors.forename: Mi Hee
authors.initials: MH
authors.lastname: Lim
authors.forename: William W
authors.initials: WW
authors.lastname: Brennessel
authors.forename: Michael R
authors.initials: MR
authors.lastname: Bukowski
authors.forename: Audria
authors.initials: A
authors.lastname: Stubna
authors.forename: Eckard
authors.initials: E
authors.lastname: Münck
authors.forename: Wonwoo
authors.initials: W
authors.lastname: Nam
authors.forename: Lawrence
authors.initials: L
authors.lastname: Que
mesh_terms: D002384:Catalysis; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D003460:Crystallization; D018360:Crystallography, X-Ray; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization; D015204:Spectroscopy, Mossbauer
chemical_list: D008024:Ligands; C066317:ferryl iron; D007501:Iron; D010100:Oxygen