title: N-O bond homolysis of an iron(II) TEMPO complex yields an iron(III) oxo intermediate.
abstract: The reaction of TEMPO with the iron(I) synthon PhB(MesIm)(3)Fe(COE) leads to formation of the κ(1)-TEMPO complex PhB(MesIm)(3)Fe(TEMPO). Structural and spectroscopic data establish the complex contains divalent iron bound to a nitroxido anion and is isoelectronic to an iron(II) peroxo complex. Thermolysis of the complex results in N-O bond homolysis, leading to the formation of an iron(III) oxo intermediate. The oxo intermediate is active in oxygen atom transfer reactions and can be trapped by the triphenylmethyl radical to give the iron(II) alkoxo complex PhB(MesIm)(3)Fe(OCPh(3)).
authors.affiliation: Department of Chemistry and Biochemistry, New Mexico State University, Las Cruces New Mexico 88003, USA. jesmith@nmsu.edu
authors.forename: Jeremy M
authors.initials: JM
authors.lastname: Smith
authors.forename: Derick E
authors.initials: DE
authors.lastname: Mayberry
authors.forename: Charles G
authors.initials: CG
authors.lastname: Margarit
authors.forename: Jörg
authors.initials: J
authors.lastname: Sutter
authors.forename: Haobin
authors.initials: H
authors.lastname: Wang
authors.forename: Karsten
authors.initials: K
authors.lastname: Meyer
authors.forename: Ranko P
authors.initials: RP
authors.lastname: Bontchev
mesh_terms: D003497:Cyclic N-Oxides / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry
chemical_list: D003497:Cyclic N-Oxides; D007501:Iron; D010100:Oxygen; C003959:TEMPO