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-system of Boreskov Institute of Catalysis

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 Full article

Journal

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

Output data

Year: 2017, Volume: 679, Pages: 193-199 Pages count : 7 DOI: 10.1016/j.cplett.2017.05.002

Tags

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

Authors

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

Affiliations

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

Funding (2)

1	Russian Science Foundation	14-13-01155
2	Russian Foundation for Basic Research	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 ANCAN OpenAlex

Full text from publisher

Submitted:	Dec 13, 2016
Accepted:	May 2, 2017
Published online:	May 6, 2017
Published print:	Jul 1, 2017

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

DB	Citing
Web of science	9
Scopus	9
Elibrary	9
OpenAlex	11