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

doi:10.1016/j.jinorgbio.2006.01.007

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

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

41 Scopus citations

Abstract

The push effect of anionic axial ligands of high-valent iron(IV)-oxo porphyrin π-cation radicals, (Porp)^{+{radical dot}}Fe^IV(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 language	English
Pages (from-to)	751-754
Number of pages	4
Journal	Journal of Inorganic Biochemistry
Volume	100
Issue number	4
DOIs	https://doi.org/10.1016/j.jinorgbio.2006.01.007
State	Published - 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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10.1016/j.jinorgbio.2006.01.007

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

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.",

keywords = "Alkane hydroxylation, Cytochrome P450, Density functional theory, High-valent iron(IV)-oxo porphyrin, Push effect",

author = "Takashi Kamachi and Tomohisa Kouno and Wonwoo Nam and Kazunari Yoshizawa",

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. ",

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doi = "10.1016/j.jinorgbio.2006.01.007",

language = "English",

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T2 - A computational study

AU - Kamachi, Takashi

AU - Kouno, Tomohisa

AU - Nam, Wonwoo

AU - Yoshizawa, Kazunari

N1 - 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.

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N2 - 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.

AB - 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.

KW - Alkane hydroxylation

KW - Cytochrome P450

KW - Density functional theory

KW - High-valent iron(IV)-oxo porphyrin

KW - Push effect

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ER -

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

Abstract

Bibliographical note

Keywords

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