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Abstract:

The salt Na3[Ru(CN)5(en)]·2H2O (en = ethylenediamine) has been prepared and characterized by its IR and electronic spectral properties. The dissociation rate constant, k-L, was found to be dependent on pH, as expected from the protonation of the unbound N-site of the en ligand. From the values of k-en = 6.2 × 10-5 s-1 and k-Hen+ = 1.07 × 10-4 s-1 (25°C) and activation parameter data, as well as considering the dependence of the rate on the concentration of reactants, a dissociative mechanism was postulated. The pKa of the Hen+ ligand was shown to be 9.7 (25°C), only slightly lower than for free (aqueous) Hen+ (9.98). The formation rate constants, kL, were determined for L = en (0.89 M-1 s-1) and L = Hen+ (0.83 M-1 s-1); the kinetic analysis suggests an ion pair-dissociative interchange mechanism, as well as the action of solvation effects. From k-L and kL, values of the stability constants, Kst (M-1), were calculated. A comparative discussion is made with the aid of data from related complexes of the [Ru(CN)5L]n- and [Fe(CN)5L]n- series. © 1989.

Registro:

Documento: Artículo
Título:Substitution kinetics in the complexes of pentacyanoruthenate(II) with ethylenediamine
Autor:Tokman, A.L.; Gentil, L.A.; Olabe, J.A.
Filiación:Departamentos de Química y de Ingeniería Química, Universidad Nacional de Mar del Plata, 7600 Mar del Plata, Argentina
Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellon 2, Ciudad Universitaria, 1428 Capital Federal, Argentina
Año:1989
Volumen:8
Número:17
Página de inicio:2091
Página de fin:2097
DOI: http://dx.doi.org/10.1016/S0277-5387(00)80340-X
Título revista:Polyhedron
Título revista abreviado:Polyhedron
ISSN:02775387
CODEN:PLYHD
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_02775387_v8_n17_p2091_Tokman

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Citas:

---------- APA ----------
Tokman, A.L., Gentil, L.A. & Olabe, J.A. (1989) . Substitution kinetics in the complexes of pentacyanoruthenate(II) with ethylenediamine. Polyhedron, 8(17), 2091-2097.
http://dx.doi.org/10.1016/S0277-5387(00)80340-X
---------- CHICAGO ----------
Tokman, A.L., Gentil, L.A., Olabe, J.A. "Substitution kinetics in the complexes of pentacyanoruthenate(II) with ethylenediamine" . Polyhedron 8, no. 17 (1989) : 2091-2097.
http://dx.doi.org/10.1016/S0277-5387(00)80340-X
---------- MLA ----------
Tokman, A.L., Gentil, L.A., Olabe, J.A. "Substitution kinetics in the complexes of pentacyanoruthenate(II) with ethylenediamine" . Polyhedron, vol. 8, no. 17, 1989, pp. 2091-2097.
http://dx.doi.org/10.1016/S0277-5387(00)80340-X
---------- VANCOUVER ----------
Tokman, A.L., Gentil, L.A., Olabe, J.A. Substitution kinetics in the complexes of pentacyanoruthenate(II) with ethylenediamine. Polyhedron. 1989;8(17):2091-2097.
http://dx.doi.org/10.1016/S0277-5387(00)80340-X