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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todo:paper_00201669_v35_n13_p3897_Estrin2023-10-03T14:16:43Z Theoretical and experimental study of medium effects on the structure and spectroscopy of the [Fe(CN)5NO]2- ion Estrin, D.A. Baraldo, L.M. Slep, L.D. Barja, B.C. Olabe, J.A. Paglieri, L. Corongiu, G. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00201669_v35_n13_p3897_Estrin |
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Universidad de Buenos Aires |
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I-28 |
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R-134 |
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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. |
| format |
JOUR |
| author |
Estrin, D.A. Baraldo, L.M. Slep, L.D. Barja, B.C. Olabe, J.A. Paglieri, L. Corongiu, G. |
| spellingShingle |
Estrin, D.A. Baraldo, L.M. Slep, L.D. Barja, B.C. Olabe, J.A. Paglieri, L. Corongiu, G. Theoretical and experimental study of medium effects on the structure and spectroscopy of the [Fe(CN)5NO]2- ion |
| author_facet |
Estrin, D.A. Baraldo, L.M. Slep, L.D. Barja, B.C. Olabe, J.A. Paglieri, L. Corongiu, G. |
| author_sort |
Estrin, D.A. |
| 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 |
| url |
http://hdl.handle.net/20.500.12110/paper_00201669_v35_n13_p3897_Estrin |
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