How axial ligands control the reactivity of high-valent iron(IV)-oxo porphyrin π-cation radicals in alkane hydroxylation: A computational study

Takashi Kamachi, Tomohisa Kouno, Wonwoo Nam, Kazunari Yoshizawa

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Abstract

The push effect of anionic axial ligands of high-valent iron(IV)-oxo porphyrin π-cation radicals, (Porp)+{radical dot}FeIV(O)(X) (X = OH-, AcO-, Cl-, and CF3 SO3-), in alkane hydroxylation is investigated by B3LYP DFT calculations. The electron-donating ability of anionic axial ligands influences the activation energy for the alkane hydroxylation by the iron(IV)-oxo intermediates and the Fe-O bond distance of the iron-oxo species in transition state.

Original languageEnglish
Pages (from-to)751-754
Number of pages4
JournalJournal of Inorganic Biochemistry
Volume100
Issue number4
DOIs
StatePublished - Apr 2006

Bibliographical note

Funding Information:
K.Y. acknowledges the Nanotechnology Support Project of the Ministry of Culture, Sports, Science and Technology of Japan (MEXT), the Joint Project of Materials Synthesis of MEXT, and CREST of Japan Science and Technology Cooperation for their support of this work. W.N. is supported by the Ministry of Science and Technology of Korea through Creative Research Initiative Program.

Keywords

  • Alkane hydroxylation
  • Cytochrome P450
  • Density functional theory
  • High-valent iron(IV)-oxo porphyrin
  • Push effect

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