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
Science article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| 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