Theoretical and experimental study of medium effects on the structure and spectroscopy of the [Fe(CN)5NO]2- ion

The influence of the solvent on the structure and IR spectrum of the [Fe(CN)5NO]2- ion is investigated by using gradient corrected density functional theory. IR spectra are also measured on different solvents and the results obtained are compared with the predicted ones. We have treated the solvent...

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Autores principales: Estrin, Dario Ariel, Baraldo Victorica, Luis Mario, Slep, Leonardo Daniel, Barja, Beatriz Carmen, Olabe Iparraguirre, Jose Antonio
Publicado: 1996
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v35_n13_p3897_Estrin
http://hdl.handle.net/20.500.12110/paper_00201669_v35_n13_p3897_Estrin
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_00201669_v35_n13_p3897_Estrin
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spelling paper:paper_00201669_v35_n13_p3897_Estrin2023-06-08T14:40:24Z Theoretical and experimental study of medium effects on the structure and spectroscopy of the [Fe(CN)5NO]2- ion Estrin, Dario Ariel Baraldo Victorica, Luis Mario Slep, Leonardo Daniel Barja, Beatriz Carmen Olabe Iparraguirre, Jose Antonio The influence of the solvent on the structure and IR spectrum of the [Fe(CN)5NO]2- ion is investigated by using gradient corrected density functional theory. IR spectra are also measured on different solvents and the results obtained are compared with the predicted ones. We have treated the solvent effects with a continuum model, based on the Onsager's reaction field approach; in order to mimic strong specific interactions, calculations were also performed on the complex protonated at the cyanide trans to the nitrosyl group. The reaction field calculations predict only qualitatively the most important observed trends, e.g., the shifts in the nitrosyl stretching wavenumber, but fail in accounting quantitatively for the differences between the spectra in water and acetonitrile. The possible role of specific interactions is consistently accounted for by interpreting the experimental shifts of the NO stretching wavenumber ν(NO), as well as the visible absorption energies, when changing the Lewis acidity of the solvent, as measured by the Gutmann's acceptor number. Ligand population analysis was performed to relate the solvent effects with the σ donor and π acceptor behavior of cyanide and nitrosyl ligands. The significance of ν(NO) shifts as a result of changes in the medium is discussed in view of the physiological relevance of transition-metal nitrosyl chemistry. Fil:Estrin, D.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Baraldo, L.M. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Slep, L.D. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Barja, B.C. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Olabe, J.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 1996 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v35_n13_p3897_Estrin http://hdl.handle.net/20.500.12110/paper_00201669_v35_n13_p3897_Estrin
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description The influence of the solvent on the structure and IR spectrum of the [Fe(CN)5NO]2- ion is investigated by using gradient corrected density functional theory. IR spectra are also measured on different solvents and the results obtained are compared with the predicted ones. We have treated the solvent effects with a continuum model, based on the Onsager's reaction field approach; in order to mimic strong specific interactions, calculations were also performed on the complex protonated at the cyanide trans to the nitrosyl group. The reaction field calculations predict only qualitatively the most important observed trends, e.g., the shifts in the nitrosyl stretching wavenumber, but fail in accounting quantitatively for the differences between the spectra in water and acetonitrile. The possible role of specific interactions is consistently accounted for by interpreting the experimental shifts of the NO stretching wavenumber ν(NO), as well as the visible absorption energies, when changing the Lewis acidity of the solvent, as measured by the Gutmann's acceptor number. Ligand population analysis was performed to relate the solvent effects with the σ donor and π acceptor behavior of cyanide and nitrosyl ligands. The significance of ν(NO) shifts as a result of changes in the medium is discussed in view of the physiological relevance of transition-metal nitrosyl chemistry.
author Estrin, Dario Ariel
Baraldo Victorica, Luis Mario
Slep, Leonardo Daniel
Barja, Beatriz Carmen
Olabe Iparraguirre, Jose Antonio
spellingShingle Estrin, Dario Ariel
Baraldo Victorica, Luis Mario
Slep, Leonardo Daniel
Barja, Beatriz Carmen
Olabe Iparraguirre, Jose Antonio
Theoretical and experimental study of medium effects on the structure and spectroscopy of the [Fe(CN)5NO]2- ion
author_facet Estrin, Dario Ariel
Baraldo Victorica, Luis Mario
Slep, Leonardo Daniel
Barja, Beatriz Carmen
Olabe Iparraguirre, Jose Antonio
author_sort Estrin, Dario Ariel
title Theoretical and experimental study of medium effects on the structure and spectroscopy of the [Fe(CN)5NO]2- ion
title_short Theoretical and experimental study of medium effects on the structure and spectroscopy of the [Fe(CN)5NO]2- ion
title_full Theoretical and experimental study of medium effects on the structure and spectroscopy of the [Fe(CN)5NO]2- ion
title_fullStr Theoretical and experimental study of medium effects on the structure and spectroscopy of the [Fe(CN)5NO]2- ion
title_full_unstemmed Theoretical and experimental study of medium effects on the structure and spectroscopy of the [Fe(CN)5NO]2- ion
title_sort theoretical and experimental study of medium effects on the structure and spectroscopy of the [fe(cn)5no]2- ion
publishDate 1996
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v35_n13_p3897_Estrin
http://hdl.handle.net/20.500.12110/paper_00201669_v35_n13_p3897_Estrin
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