title: Stable N-bridged diiron (IV) phthalocyanine cation radical complexes: synthesis and properties.
abstract: Oxidation of N-bridged diiron tetra-tert-butylphthalocyanine (FePc(t)Bu)(2)N with (t)BuOOH in halogenated solvents afforded mu-nitrido diiron (IV) phthalocyanine cation radical complexes, (X)PcFe(IV)-N-Fe(IV)Pc(+) (X) (X = Cl, Br), as evidenced by UV-vis, electron paramagnetic resonance (EPR), electrospray ionization mass spectrometry (ESI-MS), Mössbauer, X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data. Continuous introduction ESI-MS showed the initial formation of the t-butylperoxo diiron complex (t)BuOO-(FePc(t)Bu)(2)N followed by intermediate formation of a monohalogenated adduct which gave the dihalogenated complex as final stable product. Fe K-edge EXAFS analysis of (X)PcFe(IV)-N-Fe(IV)Pc(+) (X) showed bridging N atom at a distance of 1.69(1) A. The distance between two equivalent hexacoordinated in-plane iron (IV) centers is 3.39(1) A. Fe-X bond lengths are 2.33 and 2.54 A for X = Cl and Br, respectively. The use of (Cl)PcFe(IV)-N-Fe(IV)Pc(+) (Cl) for the catalytic oxidation of organic substrates has been shown for the first time.
authors.affiliation: Institut de Recherches sur la Catalyse et l'Environnement de Lyon (IRCELYON), UMR 5256, CNRS-Université Lyon 1, 2, av. A. Einstein, 69626, Villeurbanne Cedex, France.
authors.forename: Pavel
authors.initials: P
authors.lastname: Afanasiev
authors.forename: Denis
authors.initials: D
authors.lastname: Bouchu
authors.forename: Evgeny V
authors.initials: EV
authors.lastname: Kudrik
authors.forename: Jean-Marc M
authors.initials: JM
authors.lastname: Millet
authors.forename: Alexander B
authors.initials: AB
authors.lastname: Sorokin
mesh_terms: D001966:Bromine / Q000737:chemistry; D002384:Catalysis; D002713:Chlorine / Q000737:chemistry; D005290:Ferric Compounds / Q000737:chemistry*; D006873:Hydroquinones / Q000737:chemistry; D007211:Indoles / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D054833:Isoindoles; D008623:Mercaptoethanol / Q000737:chemistry; D010084:Oxidation-Reduction
chemical_list: D005290:Ferric Compounds; D006873:Hydroquinones; D007211:Indoles; D054833:Isoindoles; D002713:Chlorine; D008623:Mercaptoethanol; D007501:Iron; D001966:Bromine; C013647:phthalocyanine; C031927:hydroquinone