Abstract:
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.
Registro:
| Documento: |
Artículo
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| Título: | Structure and Bonding in Pentacyano(L)ferrate(II) and Pentacyano(L)ruthenate(II) Complexes (L = Pyridine, Pyrazine, and N-Methylpyrazinium): A Density Functional Study |
| Autor: | Estrin, D.A.; Yasmine Hamra, O.; Paglieri, L.; Slep, L.D.; Olabe, J.A. |
| Filiación: | Depto. de Quim. Inorgánica, INQUIMAE, Ciudad Universitaria-Pab II, 1428 Buenos Aires, Argentina
Ctro. Ric., Sviluppo/Stud. Sup. S., P.O. Box 1048, 09100 Cagliari, Italy
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| Año: | 1996
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| Volumen: | 35
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| Número: | 23
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| Página de inicio: | 6832
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| Página de fin: | 6837
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| Título revista: | Inorganic Chemistry
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| Título revista abreviado: | Inorg. Chem.
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| ISSN: | 00201669
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| CODEN: | INOCA
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| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v35_n23_p6832_Estrin |
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Citas:
---------- APA ----------
Estrin, D.A., Yasmine Hamra, O., Paglieri, L., Slep, L.D. & Olabe, J.A.
(1996)
. Structure and Bonding in Pentacyano(L)ferrate(II) and Pentacyano(L)ruthenate(II) Complexes (L = Pyridine, Pyrazine, and N-Methylpyrazinium): A Density Functional Study. Inorganic Chemistry, 35(23), 6832-6837.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v35_n23_p6832_Estrin [ ]
---------- CHICAGO ----------
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"
. Inorganic Chemistry 35, no. 23
(1996) : 6832-6837.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v35_n23_p6832_Estrin [ ]
---------- MLA ----------
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"
. Inorganic Chemistry, vol. 35, no. 23, 1996, pp. 6832-6837.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v35_n23_p6832_Estrin [ ]
---------- VANCOUVER ----------
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. Inorg. Chem. 1996;35(23):6832-6837.
Available from: https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v35_n23_p6832_Estrin [ ]
