Modeling the Gas-Phase Reduction of Nitrobenzene to Nitrosobenzene by Iron Monoxide: A Density Functional Theory Study | Sciact - CRIS-система Института катализа

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

Журнал

The Journal of Physical Chemistry A
ISSN: 1089-5639 , E-ISSN: 1520-5215

Вых. Данные

Год: 2004, Том: 108, Номер: 22, Страницы: 4878-4886 Страниц : 9 DOI: 10.1021/jp037351v

Ключевые слова

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

Авторы

Zilberberg Igor ¹ , Ilchenko Mykola ² , Isayev Olexandr ³ , Gorb Leonid ³ , Leszczynski Jerzy ³

Организации

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

Информация о финансировании (4)

1	National Science Foundation	300423-190200-21000
2	United States Army Research Laboratory	DAAH04-95-2-0003/DAAH04-95-C-0008
3	Совет по грантам Президента Российской Федерации	НШ-1140.2003.3
4	Сибирское отделение Российской академии наук	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 CAPlusCA OpenAlex

Поступила в редакцию:	4 нояб. 2003 г.
Принята к публикации:	13 мар. 2004 г.
Опубликована online:	11 мая 2004 г.
Опубликована в печати:	1 июн. 2004 г.

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

БД	Цитирований
Web of science	12
Scopus	13
РИНЦ	13
OpenAlex	15