Modeling the Gas-Phase Reduction of Nitrobenzene to Nitrosobenzene by Iron Monoxide: A Density Functional Theory Study | Sciact - CRIS-system of Boreskov Institute of Catalysis

Modeling the Gas-Phase Reduction of Nitrobenzene to Nitrosobenzene by Iron Monoxide: A Density Functional Theory Study Full article

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

Tags

ELECTRONIC-STRUCTURE; CORRELATION-ENERGY; TRANSITION-METALS; OXYGEN MOLECULES; INFRARED-SPECTRA; FeO; ATOMS; THERMOCHEMISTRY; EXCHANGE; REPRESENTATION

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	National Science Foundation	300423-190200-21000
2	United States Army Research Laboratory	DAAH04-95-2-0003/DAAH04-95-C-0008
3	Council for Grants of the President of the Russian Federation	НШ-1140.2003.3
4	Siberian Branch of the Russian Academy of Sciences	4.1.16

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.

Zilberberg I. , Ilchenko M. , Isayev O. , Gorb L. , Leszczynski J.
Modeling the Gas-Phase Reduction of Nitrobenzene to Nitrosobenzene by Iron Monoxide: A Density Functional Theory Study
The Journal of Physical Chemistry A. 2004. V.108. N22. P.4878-4886. DOI: 10.1021/jp037351v WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Nov 4, 2003
Accepted:	Mar 13, 2004
Published online:	May 11, 2004
Published print:	Jun 1, 2004

Web of science:	WOS:000221700100009
Scopus:	2-s2.0-2942704067
Elibrary:	13450747
Chemical Abstracts:	2004:377224
Chemical Abstracts (print):	141:106041
OpenAlex:	W1984327540

DB	Citing
Web of science	12
Scopus	13
Elibrary	13
OpenAlex	15