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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todo:paper_00201669_v35_n23_p6832_Estrin2023-10-03T14:16:44Z 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, D.A. Yasmine Hamra, O. Paglieri, L. Slep, L.D. Olabe, J.A. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00201669_v35_n23_p6832_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 |
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. |
| format |
JOUR |
| author |
Estrin, D.A. Yasmine Hamra, O. Paglieri, L. Slep, L.D. Olabe, J.A. |
| spellingShingle |
Estrin, D.A. Yasmine Hamra, O. Paglieri, L. Slep, L.D. Olabe, J.A. 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, D.A. Yasmine Hamra, O. Paglieri, L. Slep, L.D. Olabe, J.A. |
| author_sort |
Estrin, D.A. |
| 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 |
| url |
http://hdl.handle.net/20.500.12110/paper_00201669_v35_n23_p6832_Estrin |
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