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

被引：42

作者：

Kamachi, Takashi

Kouno, Tomohisa

Nam, Wonwoo ^{[1
]}

Yoshizawa, Kazunari

机构：

[1] Kyushu Univ, Inst Mat Chem, Fukuoka 8128581, Japan

[2] Ewha Womans Univ, Dept Chem, Div Nano Sci, Seoul 120750, South Korea

[3] Ewha Womans Univ, Ctr Biomimet Syst, Seoul 120750, South Korea

来源：

JOURNAL OF INORGANIC BIOCHEMISTRY | 2006年 / 100卷 / 04期

关键词：

alkane hydroxylation; density functional theory; cytochrome P450; high-valent iron(IV)-oxo porphyrin; push effect;

D O I：

10.1016/j.jinorgbio.2006.01.007

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

The push effect of anionic axial ligands of high-valent iron(IV)-oxo porphyrin pi-cation radicals, (Porp)(+)-Fe-IV(0)(X) (X = OH-, AcO-, Cl-. and CF3SO3-), 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. (c) 2006 Elsevier Inc. All rights reserved.

引用

页码：751 / 754

页数：4

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