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 | Sciact - CRIS-система Института катализа

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 Научная публикация

Журнал

Chemical Physics Letters
ISSN: 0009-2614 , E-ISSN: 1873-4448

Вых. Данные

Год: 2017, Том: 679, Страницы: 193-199 Страниц : 7 DOI: 10.1016/j.cplett.2017.05.002

Ключевые слова

HYDROGEN-ATOM TRANSFER; CATALYTIC-OXIDATION; PAIRED ORBITALS; HYDROXIDE; ENZYMES; WATER; DETERMINANT; PREDICTIONS; CHEMISTRY; DIOXYGEN

Авторы

Kovalskii V. ¹ , Shubin A. ^1,2 , Chen Y. ³ , Ovchinnikov D. ¹ , Ruzankin S.Ph. ¹ , Hasegawa J. ³ , Zilberberg I. ^1,2 , Parmon V.N. ^1,2

Организации

1	Boreskov Institute of Catalysis, Novosibirsk 630090, Russian Federation
2	Novosibirsk State University, Novosibirsk 630090, Russian Federation
3	Institute for Catalysis, Hokkaido University, Kita 21, Nishi 10, Kita-ku, Sapporo, Hokkaido 001-0021, Japan

Информация о финансировании (2)

1	Российский научный фонд	14-13-01155
2	Российский фонд фундаментальных исследований	15-29-01275

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=O and the oxyl state correlates with the energy barrier of the H-abstraction from methane

Kovalskii V. , Shubin A. , Chen Y. , Ovchinnikov D. , Ruzankin S.P. , Hasegawa J. , Zilberberg I. , Parmon V.N.
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. 2017. V.679. P.193-199. DOI: 10.1016/j.cplett.2017.05.002 WOS Scopus РИНЦ CAPlusCA OpenAlex

Полный текст от издателя

Поступила в редакцию:	13 дек. 2016 г.
Принята к публикации:	2 мая 2017 г.
Опубликована online:	6 мая 2017 г.
Опубликована в печати:	1 июл. 2017 г.

Web of science:	WOS:000405403900031
Scopus:	2-s2.0-85019054000
РИНЦ:	31039680
Chemical Abstracts:	2017:762432
Chemical Abstracts (print):	167:107910
OpenAlex:	W2610381005

БД	Цитирований
Web of science	11
Scopus	11
РИНЦ	9
OpenAlex	13