title: Probing the cytochrome P450-like reactivity of high-valent oxo iron intermediates in the gas phase.
abstract: Electrospray ionization in combination with Fourier transform ion cyclotron resonance spectrometry is used to prepare and characterize at a molecular level high-valent oxoiron intermediates formed in the reaction of [(TPFPP)Fe(III)]Cl (TPFPP= meso-tetrakis(pentafluorophenyl)porphinato dianion) (1-Cl) with H(2)O(2) in methanol. The intrinsic reactivity in the gas phase of the iron(IV) oxo porphyrin cation radical complex, [(TPFPP)(.+)Fe(IV)=O](+), has been probed toward selected substrates (S), chosen among naturally occurring and model compounds. Whereas CO and cyclohexane proved to be unreactive, olefins, sulfides, amines, and phosphites all undergo oxygen atom transfer in the gas phase yielding the reduction product 1 and/or an adduct ion ([1-S](+)). The reaction efficiencies show a qualitative correlation with the oxophilic character of the active site of S. A notable exception is nitric oxide, which displays a remarkably high reactivity, in line with the important role of NO reactions with iron porphyrin complexes. Furthermore, subsidiary information on the neat association reaction of 1 with selected ligands (L) has been obtained by a kinetic study showing that both the efficiency and the extent of ligation toward the naked ion 1 depend on the electron-donating ability of L.
authors: Dipartimento di Studi di Chimica e Tecnologia delle Sostanze Biologicamente Attive, Università di Roma "La Sapienza", P.le A. Moro 5, I-00185 Roma, Italy. mariaelisa.crestoni@uniroma1.it
authors: M Elisa
authors: ME
authors: Crestoni
authors: S
authors: S
authors: Fornarini
mesh_terms: D003577:Cytochrome P-450 Enzyme System / Q000737:chemistry*; D005290:Ferric Compounds / Q000138:chemical synthesis*; D005583:Fourier Analysis; D005740:Gases / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry; D000432:Methanol / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods; D013997:Time Factors
chemical_list: D005290:Ferric Compounds; D005740:Gases; D009942:Organometallic Compounds; D003577:Cytochrome P-450 Enzyme System; D006861:Hydrogen Peroxide; D000432:Methanol