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Abstract:

The mixed-valence, cyanide-bridged complexes K5[(NC)jMII-CN-RuI(edta)] (M = Fe, Ru or Os; edta = ethylenedinitrilotetraacetate) were prepared by mixing the hexacyanide species with a solution of [Ru(edta)(H 22 O)]~. The complexes were characterized by chemical analysis, IR, Raman and VIS/NIR spectroscopy. They show an intense band in the 600-1000 nm region (dependent on M), associated with an intervalence (i.v.) transition from M to Ru1, as confirmed by electrochemical measurements of the redox potentials at both metal centres. The equilibrium constants for the formation of the binuclear species were similar for the three complexes, (1.5 ±0.1) x 103 dm3 mol1. These complexes were the predominant species in excess of free hexacyanide, but tri- and poly-nuclear species were obtained by increasing the concentration of [Ru(edta)(H 22 O)]~, as demonstrated through the electronic spectral shifts of the i.v. band and the redox potentials of the M couples, which were indicative of Ru(edta) co-ordination to the exposed nitrogen ends of cyanides in the precursor binuclear complexes. The kinetics of formation and dissociation of the binuclear complexes were also measured, with k, and kA showing values nearly independent of.M (ca. 10 dm3 mol1 s1 and 8 x 10~3 s1 respectively, at 25.0 °C, /= 0.1 mol dnT3), suggesting thé onset of associative mechanisms. The Hush model showed the three complexes to adopt a valence-trapped behaviour, with a moderate coupling between the metal centres.

Registro:

Documento: Artículo
Título:Mixed-valence cyano-bridged complexes containing [M(CN)6]4 (M = Fe, Ru or Os) and [Runi(edta)]~ (edta = ethylenedinitrilotetraacetate): Synthesis, spectroscopic and kinetic characterization
Autor:Forlano, P.; Cukiernik, F.D.; Poizat, O.; José, A.; Olabe
Filiación:Departamcnto de Qiiitnica Inorgänica, Analiticay Quimica, Fisica
Facultad de Ciencias Exact as Y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellôn II, 1428 Buenos Aires, Argentina
Año:1997
Número:9
Página de inicio:1595
Página de fin:1599
Título revista:Journal of the Chemical Society - Dalton Transactions
ISSN:03009246
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_03009246_v_n9_p1595_Forlano

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Citas:

---------- APA ----------
Forlano, P., Cukiernik, F.D., Poizat, O., José, A. & Olabe (1997) . Mixed-valence cyano-bridged complexes containing [M(CN)6]4 (M = Fe, Ru or Os) and [Runi(edta)]~ (edta = ethylenedinitrilotetraacetate): Synthesis, spectroscopic and kinetic characterization. Journal of the Chemical Society - Dalton Transactions(9), 1595-1599.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_03009246_v_n9_p1595_Forlano [ ]
---------- CHICAGO ----------
Forlano, P., Cukiernik, F.D., Poizat, O., José, A., Olabe "Mixed-valence cyano-bridged complexes containing [M(CN)6]4 (M = Fe, Ru or Os) and [Runi(edta)]~ (edta = ethylenedinitrilotetraacetate): Synthesis, spectroscopic and kinetic characterization" . Journal of the Chemical Society - Dalton Transactions, no. 9 (1997) : 1595-1599.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_03009246_v_n9_p1595_Forlano [ ]
---------- MLA ----------
Forlano, P., Cukiernik, F.D., Poizat, O., José, A., Olabe "Mixed-valence cyano-bridged complexes containing [M(CN)6]4 (M = Fe, Ru or Os) and [Runi(edta)]~ (edta = ethylenedinitrilotetraacetate): Synthesis, spectroscopic and kinetic characterization" . Journal of the Chemical Society - Dalton Transactions, no. 9, 1997, pp. 1595-1599.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_03009246_v_n9_p1595_Forlano [ ]
---------- VANCOUVER ----------
Forlano, P., Cukiernik, F.D., Poizat, O., José, A., Olabe Mixed-valence cyano-bridged complexes containing [M(CN)6]4 (M = Fe, Ru or Os) and [Runi(edta)]~ (edta = ethylenedinitrilotetraacetate): Synthesis, spectroscopic and kinetic characterization. 1997(9):1595-1599.
Available from: https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_03009246_v_n9_p1595_Forlano [ ]