Modeling the Gas-Phase Reduction of Nitrobenzene to Nitrosobenzene by Iron Monoxide:
A Density Functional Theory Study
Full article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| Journal |
The Journal of Physical Chemistry A
ISSN: 1089-5639
, E-ISSN: 1520-5215
|
| Output data |
Year: 2004,
Volume: 108,
Number: 22,
Pages: 4878-4886
Pages count
: 9
DOI:
10.1021/jp037351v
|
| Authors |
Zilberberg Igor
1
,
Ilchenko Mykola
2
,
Isayev Olexandr
3
,
Gorb Leonid
3
,
Leszczynski Jerzy
3
|
| Affiliations |
| 1 |
Boreskov Institute of Catalysis, Novosibirsk 630090, Russia
|
| 2 |
Institute of Cell Biology and Genetic Engineering, NAS of Ukraine, pr. Zabolotnogo, 148, Kiev 03143, Ukraine
|
| 3 |
Computational Center for Molecular Structure and Interaction, Department of Chemistry, Jackson State University, Jackson, Mississippi 39217-0510
|
|
Funding (4)
|
1
|
Council for Grants of the President of the Russian Federation
|
НШ-1140.2003.3
|
|
2
|
Президиум СО РАН
|
4.1.16
|
|
3
|
United States Army Research Laboratory
|
DAAH04-95-2-0003/DAAH04-95-C-0008
|
|
4
|
National Science Foundation
|
300423-190200-21000
|
The gas-phase selective reduction of nitrobenzene (NB) to nitrosobenzene (NSB) by iron monoxide has been for the first time studied by means of density functional theory (DFT) using both the hybrid and pure exchange-correlation functionals. As shown at both DFT levels, when interacting with NB, the iron center donates an electron into the nitro group to form the NB- anion radical strongly coupled by FeO+. This electron-transfer characteristic of the NB-−FeO+ intermediate reveals itself in the S2 operator expectation value that exceeds its eigenvalue of S(S + 1) by almost 1.0. Further reaction steps necessary to obtain nitrosobenzene from this intermediate are discussed. One of the possible steps based on the abstraction of oxygen from the nitro group by a ferrous center is considered in detail. This reaction appears to be favorable at the pure DFT level, whereas the hybrid theory predicts small endothermicity for the process.