Structure and Bonding in Pentacyano(L)ferrate(II) and Pentacyano(L)ruthenate(II) Complexes (L = Pyridine, Pyrazine, and N-Methylpyrazinium): A Density Functional Study

Density Functional Theory (DFT) at the generalized gradient approximation (GGA) level has been applied to the complexes [Fe(CN)5L]n- and [Ru(CN)5L]n- (L = pyridine, pyrazine, N-methylpyrazinium), as well as to [Fe(CN)5]3- and [Ru(CN)5]3-. Full geometry optimizations have been performed in all cases....

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Autores principales: Estrin, Dario Ariel, Slep, Leonardo Daniel, Olabe Iparraguirre, Jose Antonio
Publicado: 1996
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v35_n23_p6832_Estrin
http://hdl.handle.net/20.500.12110/paper_00201669_v35_n23_p6832_Estrin
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling paper:paper_00201669_v35_n23_p6832_Estrin2023-06-08T14:40:25Z Structure and Bonding in Pentacyano(L)ferrate(II) and Pentacyano(L)ruthenate(II) Complexes (L = Pyridine, Pyrazine, and N-Methylpyrazinium): A Density Functional Study Estrin, Dario Ariel Slep, Leonardo Daniel Olabe Iparraguirre, Jose Antonio Density Functional Theory (DFT) at the generalized gradient approximation (GGA) level has been applied to the complexes [Fe(CN)5L]n- and [Ru(CN)5L]n- (L = pyridine, pyrazine, N-methylpyrazinium), as well as to [Fe(CN)5]3- and [Ru(CN)5]3-. Full geometry optimizations have been performed in all cases. The geometrical parameters are in good agreement with available information for related systems. The role of the MII-L back-bonding was investigated by means of a L and cyanide Mulliken population analysis. For both Fe(II) and Ru(II) complexes the metal-L dissociation energies follow the ordering pyridine < pyrazine < N-methyl pyrazinium, consistent with the predicted σ-donating and π*-accepting abilities of the L ligands. Also, the computed metal-L bond dissociation energies are systematically smaller in the Ru(II) than in the Fe(II) complexes. This fact suggests that previous interpretations of kinetic data, showing that ruthenium complexes in aqueous solution are more inert than their iron analogues, are not related to a stronger Ru-L bond but are probably due to solvation effects. Fil:Estrin, D.A. 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: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_n23_p6832_Estrin http://hdl.handle.net/20.500.12110/paper_00201669_v35_n23_p6832_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 Density Functional Theory (DFT) at the generalized gradient approximation (GGA) level has been applied to the complexes [Fe(CN)5L]n- and [Ru(CN)5L]n- (L = pyridine, pyrazine, N-methylpyrazinium), as well as to [Fe(CN)5]3- and [Ru(CN)5]3-. Full geometry optimizations have been performed in all cases. The geometrical parameters are in good agreement with available information for related systems. The role of the MII-L back-bonding was investigated by means of a L and cyanide Mulliken population analysis. For both Fe(II) and Ru(II) complexes the metal-L dissociation energies follow the ordering pyridine < pyrazine < N-methyl pyrazinium, consistent with the predicted σ-donating and π*-accepting abilities of the L ligands. Also, the computed metal-L bond dissociation energies are systematically smaller in the Ru(II) than in the Fe(II) complexes. This fact suggests that previous interpretations of kinetic data, showing that ruthenium complexes in aqueous solution are more inert than their iron analogues, are not related to a stronger Ru-L bond but are probably due to solvation effects.
author Estrin, Dario Ariel
Slep, Leonardo Daniel
Olabe Iparraguirre, Jose Antonio
spellingShingle Estrin, Dario Ariel
Slep, Leonardo Daniel
Olabe Iparraguirre, Jose Antonio
Structure and Bonding in Pentacyano(L)ferrate(II) and Pentacyano(L)ruthenate(II) Complexes (L = Pyridine, Pyrazine, and N-Methylpyrazinium): A Density Functional Study
author_facet Estrin, Dario Ariel
Slep, Leonardo Daniel
Olabe Iparraguirre, Jose Antonio
author_sort Estrin, Dario Ariel
title Structure and Bonding in Pentacyano(L)ferrate(II) and Pentacyano(L)ruthenate(II) Complexes (L = Pyridine, Pyrazine, and N-Methylpyrazinium): A Density Functional Study
title_short Structure and Bonding in Pentacyano(L)ferrate(II) and Pentacyano(L)ruthenate(II) Complexes (L = Pyridine, Pyrazine, and N-Methylpyrazinium): A Density Functional Study
title_full Structure and Bonding in Pentacyano(L)ferrate(II) and Pentacyano(L)ruthenate(II) Complexes (L = Pyridine, Pyrazine, and N-Methylpyrazinium): A Density Functional Study
title_fullStr Structure and Bonding in Pentacyano(L)ferrate(II) and Pentacyano(L)ruthenate(II) Complexes (L = Pyridine, Pyrazine, and N-Methylpyrazinium): A Density Functional Study
title_full_unstemmed Structure and Bonding in Pentacyano(L)ferrate(II) and Pentacyano(L)ruthenate(II) Complexes (L = Pyridine, Pyrazine, and N-Methylpyrazinium): A Density Functional Study
title_sort structure and bonding in pentacyano(l)ferrate(ii) and pentacyano(l)ruthenate(ii) complexes (l = pyridine, pyrazine, and n-methylpyrazinium): a density functional study
publishDate 1996
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v35_n23_p6832_Estrin
http://hdl.handle.net/20.500.12110/paper_00201669_v35_n23_p6832_Estrin
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