DFT predictions for hydrogen atom transfer at the [FeO]2+ group: A distinct activity of the oxyl state FeIII-O

I. L. Zilberberg, A. A. Shubin, S. Ph Ruzankin, V. Yu Kovalskii, D. A. Ovchinnikov, V. N. Parmon

Результат исследования: Публикации в книгах, отчётах, сборниках, трудах конференцийстатья в сборнике материалов конференциинаучнаярецензирование

1 Цитирования (Scopus)

Аннотация

Iron (hydr)oxo complexes are becoming major subject of investigations in the field of hydrocarbon partial oxidation for industrial applications. Most challenging goal is to design the oxidation of methane to methanol as effective as the natural one-step process realized by methane monooxygenase under mild conditions. Key intermediate of iron enzymes is commonly agreed to be the complex containing the [FeO]2+ group. One may suggest that the same group on iron hydroxides would perform the same or higher reactivity toward the H-abstraction as that in enzymes. This suggestion was proved to be true by the presented DFT predictions on the methane hydrogen abstraction process at terminal Fe-oxo group in model mono-, di- and tetramer iron hydroxide clusters. The most important result obtained is a distinct activity of the radicaloid oxyl state FeIII-O as compared to ferryl state FeIV=O for the same [FeO]2+ group. If the oxyl state is ground for terminal Fe-oxo group in hydroxides, then it is more active than the same group in mono-iron enzymes complexes. Since the electron configuration of the [FeO]2+ group in various ligand environment is always a mixture of oxyl and ferryl contributions, the activity of the [FeO]2+ group is determined by the oxyl contribution.

Язык оригиналаанглийский
Название основной публикацииInternational Conference of Computational Methods in Sciences and Engineering 2016, ICCMSE 2016
РедакторыZacharoula Kalogiratou, Theodore E. Simos, Theodore Monovasilis, Theodore E. Simos, Theodore E. Simos
ИздательAmerican Institute of Physics Inc.
ISBN (электронное издание)9780735414549
DOI
СостояниеОпубликовано - 6 дек 2016
СобытиеInternational Conference of Computational Methods in Sciences and Engineering 2016, ICCMSE 2016 - Athens, Греция
Продолжительность: 17 мар 201620 мар 2016

Серия публикаций

НазваниеAIP Conference Proceedings
Том1790
ISSN (печатное издание)0094-243X
ISSN (электронное издание)1551-7616

Конференция

КонференцияInternational Conference of Computational Methods in Sciences and Engineering 2016, ICCMSE 2016
СтранаГреция
ГородAthens
Период17.03.201620.03.2016

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