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• W2056553478 endingPage "5387" @default.
• W2056553478 startingPage "5379" @default.
• W2056553478 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." @default.
• W2056553478 created "2016-06-24" @default.
• W2056553478 creator A5014553586 @default.
• W2056553478 creator A5046972661 @default.
• W2056553478 date "2005-06-11" @default.
• W2056553478 modified "2023-09-23" @default.
• W2056553478 title "Probing the Cytochrome P450-like Reactivity of High-Valent Oxo Iron Intermediates in the Gas Phase" @default.
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• W2056553478 doi "https://doi.org/10.1021/ic048595c" @default.
• W2056553478 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/16022536" @default.
• W2056553478 hasPublicationYear "2005" @default.
• W2056553478 type Work @default.

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