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Regioselectivity of aliphatic versus aromatic hydroxylation by a nonheme iron(ii)-superoxo complex

Title
Regioselectivity of aliphatic versus aromatic hydroxylation by a nonheme iron(ii)-superoxo complex
Authors
Latifi R.Tahsini L.Nam W.De Visser S.P.
Ewha Authors
남원우
SCOPUS Author ID
남원우scopus
Issue Date
2012
Journal Title
Physical Chemistry Chemical Physics
ISSN
1463-9076JCR Link
Citation
vol. 14, no. 7, pp. 2518 - 2524
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
Many enzymes in nature utilize molecular oxygen on an iron center for the catalysis of substrate hydroxylation. In recent years, great progress has been made in understanding the function and properties of iron(iv)-oxo complexes; however, little is known about the reactivity of iron(ii)-superoxo intermediates in substrate activation. It has been proposed recently that iron(ii)-superoxo intermediates take part as hydrogen abstraction species in the catalytic cycles of nonheme iron enzymes. To gain insight into oxygen atom transfer reactions by the nonheme iron(ii)-superoxo species, we performed a density functional theory study on the aliphatic and aromatic hydroxylation reactions using a biomimetic model complex. The calculations show that nonheme iron(ii)-superoxo complexes can be considered as effective oxidants in hydrogen atom abstraction reactions, for which we find a low barrier of 14.7 kcal mol -1 on the sextet spin state surface. On the other hand, electrophilic reactions, such as aromatic hydroxylation, encounter much higher (>20 kcal mol -1) barrier heights and therefore are unlikely to proceed. A thermodynamic analysis puts our barrier heights into a larger context of previous studies using nonheme iron(iv)-oxo oxidants and predicts the activity of enzymatic iron(ii)-superoxo intermediates. © 2012 the Owner Societies.
DOI
10.1039/c2cp23352e
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자연과학대학 > 화학·나노과학전공 > Journal papers
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