Hidden radical reactivity of the [FeO]2+ group in the H-abstraction from methane: DFT and CASPT2 supported mechanism by the example of model iron (hydro)oxide species

V. Kovalskii; A. Shubin; Y. Chen; D. Ovchinnikov; S. Ph Ruzankin; J. Hasegawa; I. Zilberberg; V. N. Parmon

doi:10.1016/j.cplett.2017.05.002

Hidden radical reactivity of the [FeO]²⁺ group in the H-abstraction from methane: DFT and CASPT2 supported mechanism by the example of model iron (hydro)oxide species

V. Kovalskii, A. Shubin, Y. Chen, D. Ovchinnikov, S. Ph Ruzankin, J. Hasegawa, I. Zilberberg, V. N. Parmon

Результат исследования: Научные публикации в периодических изданиях › статья › рецензирование

4 Цитирования (Scopus)

Аннотация

Reactivity of the [FeO]²⁺ group in the abstraction of hydrogen from methane is determined by metastable oxyl state Fe^III–O causing the negative spin polarization of the methyl moiety as was shown by quantum-chemical means with the use of model iron hydroxide species FeO(OH)₂, Fe₂O(OH)₅, and Fe₄O₅(OH)₃ as an example. The energy of the gap between the ground-state ferryl configuration Fe^IV[dbnd]O and the oxyl state correlates with the energy barrier of the H-abstraction from methane.

Язык оригинала	английский
Страницы (с-по)	193-199
Число страниц	7
Журнал	Chemical Physics Letters
Том	679
DOI	https://doi.org/10.1016/j.cplett.2017.05.002
Состояние	Опубликовано - 1 июл. 2017

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10.1016/j.cplett.2017.05.002

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Kovalskii, V., Shubin, A., Chen, Y., Ovchinnikov, D., Ruzankin, S. P., Hasegawa, J., Zilberberg, I., & Parmon, V. N. (2017). Hidden radical reactivity of the [FeO]²⁺ group in the H-abstraction from methane: DFT and CASPT2 supported mechanism by the example of model iron (hydro)oxide species. Chemical Physics Letters, 679, 193-199. https://doi.org/10.1016/j.cplett.2017.05.002

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title = "Hidden radical reactivity of the [FeO]2+ group in the H-abstraction from methane: DFT and CASPT2 supported mechanism by the example of model iron (hydro)oxide species",

abstract = "Reactivity of the [FeO]2+ group in the abstraction of hydrogen from methane is determined by metastable oxyl state FeIII–O causing the negative spin polarization of the methyl moiety as was shown by quantum-chemical means with the use of model iron hydroxide species FeO(OH)2, Fe2O(OH)5, and Fe4O5(OH)3 as an example. The energy of the gap between the ground-state ferryl configuration FeIV[dbnd]O and the oxyl state correlates with the energy barrier of the H-abstraction from methane.",

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Kovalskii, V, Shubin, A, Chen, Y, Ovchinnikov, D, Ruzankin, SP, Hasegawa, J, Zilberberg, I & Parmon, VN 2017, 'Hidden radical reactivity of the [FeO]²⁺ group in the H-abstraction from methane: DFT and CASPT2 supported mechanism by the example of model iron (hydro)oxide species', Chemical Physics Letters, том. 679, стр. 193-199. https://doi.org/10.1016/j.cplett.2017.05.002

Hidden radical reactivity of the [FeO]²⁺ group in the H-abstraction from methane : DFT and CASPT2 supported mechanism by the example of model iron (hydro)oxide species. / Kovalskii, V.; Shubin, A.; Chen, Y. и др.

В: Chemical Physics Letters, Том 679, 01.07.2017, стр. 193-199.

Результат исследования: Научные публикации в периодических изданиях › статья › рецензирование

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T2 - DFT and CASPT2 supported mechanism by the example of model iron (hydro)oxide species

AU - Kovalskii, V.

AU - Shubin, A.

AU - Chen, Y.

AU - Ovchinnikov, D.

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AU - Parmon, V. N.

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AB - Reactivity of the [FeO]2+ group in the abstraction of hydrogen from methane is determined by metastable oxyl state FeIII–O causing the negative spin polarization of the methyl moiety as was shown by quantum-chemical means with the use of model iron hydroxide species FeO(OH)2, Fe2O(OH)5, and Fe4O5(OH)3 as an example. The energy of the gap between the ground-state ferryl configuration FeIV[dbnd]O and the oxyl state correlates with the energy barrier of the H-abstraction from methane.

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