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Electronic Structure and Bonding of {Fe(PhNO2)}6 Complexes: A Density Functional Theory Study Full article

Journal The Journal of Physical Chemistry A
ISSN: 1089-5639 , E-ISSN: 1520-5215
Output data Year: 2007, Volume: 111, Number: 18, Pages: 3571-3576 Pages count : 6 DOI: 10.1021/jp0668798
Tags Chemical bonds; Complexation; Degradation; Density functional theory; Electronic structure; Mathematical models
Authors Isayev Olexandr 1 , Gorb L. 1 , Zilberberg Igor 2 , Leszczynski Jerzy 1
Affiliations
1 Computational Center for Molecular Structure and Interactions, Jackson State University, Jackson, Mississippi 39217
2 Boreskov Institute of Catalysis, Novosibirsk 630090, Russia

Funding (2)

1 U.S. Army Engineer Research and Development Center W912HZ-05-C-0051
2 United States Army Research Laboratory DAAD19-01-2-0014

Abstract: Reduction of nitro-aromatic compounds (NACs) proceeds through intermediates with a partial electron transfer into the nitro group from a reducing agent. To estimate the extent of such a transfer and, therefore, the activity of various model ferrous-containing reductants toward NAC degradation, the unrestricted density functional theory (DFT) in the basis of paired Lo¨wdin-Amos-Hall orbitals has been applied to complexes of nitrobenzene (NB) and model Fe(II) hydroxides including cationic [FeOH]+, then neutral Fe(OH)2, and finally anionic [Fe(OH)3]-. Electron transfer is considered to be a process of unpairing electrons (without the change of total spin projection Sz) that reveals itself in a substantial spin contamination of the unrestricted solution. The unrestricted orbitals are transformed into localized paired orbitals to determine the orbital channels for a particular electron-transfer state and the weights of idealized charge-transfer and covalent electron structures. This approach allows insight into the electronic structure and bonding of the {Fe(PhNO2)}6 unit (according to Enemark and Feltham notation) to be gained using model nitrobenzene complexes. The electronic structure of this unit can be expressed in terms of π-type covalent bonding [Fe+2(d6, S ) 2) - PhNO2(S ) 0)] or charge-transfer configuration [Fe+3(d5, S ) 5/2) - {PhNO2}- ((π*)1, S ) 1/2)].
Cite: Isayev O. , Gorb L. , Zilberberg I. , Leszczynski J.
Electronic Structure and Bonding of {Fe(PhNO2)}6 Complexes: A Density Functional Theory Study
The Journal of Physical Chemistry A. 2007. V.111. N18. P.3571-3576. DOI: 10.1021/jp0668798 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
Submitted: Oct 19, 2006
Accepted: Jan 31, 2007
Published online: Apr 19, 2007
Published print: May 1, 2007
Identifiers:
Web of science: WOS:000246189700020
Scopus: 2-s2.0-34249664859
Elibrary: 13545211
Chemical Abstracts: 2007:427949
Chemical Abstracts (print): 147:126556
OpenAlex: W2054384451
Citing:
DB Citing
Web of science 3
Scopus 3
Elibrary 3
OpenAlex 5
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