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

Fundamental Organic Chemistry

Research output: Contribution to journal › Article

33 Citations (Scopus)

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
Publication status	Published - Apr 1 2006

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Hydroxylation

Alkanes

Porphyrins

Cations

Ligands

Discrete Fourier transforms

Iron

Activation energy

Electrons

ferryl iron

hydroxide ion

All Science Journal Classification (ASJC) codes

Biochemistry
Inorganic Chemistry

Cite this

Kamachi, T., Kouno, T., Nam, W., & Yoshizawa, K. (2006). How axial ligands control the reactivity of high-valent iron(IV)-oxo porphyrin π-cation radicals in alkane hydroxylation: A computational study. Journal of Inorganic Biochemistry, 100(4), 751-754. https://doi.org/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. / Kamachi, Takashi; Kouno, Tomohisa; Nam, Wonwoo; Yoshizawa, Kazunari.

In: Journal of Inorganic Biochemistry, Vol. 100, No. 4, 01.04.2006, p. 751-754.

Research output: Contribution to journal › Article

Kamachi, T, Kouno, T, Nam, W & Yoshizawa, K 2006, 'How axial ligands control the reactivity of high-valent iron(IV)-oxo porphyrin π-cation radicals in alkane hydroxylation: A computational study', Journal of Inorganic Biochemistry, vol. 100, no. 4, pp. 751-754. https://doi.org/10.1016/j.jinorgbio.2006.01.007

Kamachi T, Kouno T, Nam W, Yoshizawa K. How axial ligands control the reactivity of high-valent iron(IV)-oxo porphyrin π-cation radicals in alkane hydroxylation: A computational study. Journal of Inorganic Biochemistry. 2006 Apr 1;100(4):751-754. https://doi.org/10.1016/j.jinorgbio.2006.01.007

Kamachi, Takashi ; Kouno, Tomohisa ; Nam, Wonwoo ; Yoshizawa, Kazunari. / How axial ligands control the reactivity of high-valent iron(IV)-oxo porphyrin π-cation radicals in alkane hydroxylation : A computational study. In: Journal of Inorganic Biochemistry. 2006 ; Vol. 100, No. 4. pp. 751-754.

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10.1016/j.jinorgbio.2006.01.007