Mechanistic insight into the aromatic hydroxylation by high-valent iron(IV)-oxo porphyrin π-cation radical complexes

Min Jung Kang, Ju Song Woon, Ah Rim Han, Young S. Choi, Ho Gyeom Jang, Wonwoo Nam

Research output: Contribution to journalArticle

49 Citations (Scopus)

Abstract

(Chemical Equation Presented) Mechanistic studies of the aromatic hydroxylation by high-valent iron(IV)-oxo porphyrin π-cation radicals revealed that the aromatic oxidation involves an initial electrophilic attack on the π-system of the aromatic ring to produce a tetrahedral radical or cationic σ-complex. The mechanism was proposed on the basis of experimental results such as a large negative Hammett ρ value and an inverse kinetic isotope effect. By carrying out isotope labeling studies, the oxygen in oxygenated products was found to derive from the iron-oxo porphyrin intermediates.

Original languageEnglish
Pages (from-to)6301-6304
Number of pages4
JournalJournal of Organic Chemistry
Volume72
Issue number16
DOIs
Publication statusPublished - 2007 Aug 1

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Hydroxylation
Porphyrins
Isotopes
Cations
Isotope Labeling
Labeling
Iron
Oxygen
Oxidation
Kinetics
ferryl iron

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Mechanistic insight into the aromatic hydroxylation by high-valent iron(IV)-oxo porphyrin π-cation radical complexes. / Kang, Min Jung; Woon, Ju Song; Han, Ah Rim; Choi, Young S.; Jang, Ho Gyeom; Nam, Wonwoo.

In: Journal of Organic Chemistry, Vol. 72, No. 16, 01.08.2007, p. 6301-6304.

Research output: Contribution to journalArticle

Kang, Min Jung ; Woon, Ju Song ; Han, Ah Rim ; Choi, Young S. ; Jang, Ho Gyeom ; Nam, Wonwoo. / Mechanistic insight into the aromatic hydroxylation by high-valent iron(IV)-oxo porphyrin π-cation radical complexes. In: Journal of Organic Chemistry. 2007 ; Vol. 72, No. 16. pp. 6301-6304.
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