Substitution kinetics in the complexes of pentacyanoruthenate(II) with ethylenediamine
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-...
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todo:paper_02775387_v8_n17_p2091_Tokman2023-10-03T15:16:12Z Substitution kinetics in the complexes of pentacyanoruthenate(II) with ethylenediamine Tokman, A.L. Gentil, L.A. Olabe, J.A. 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. 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_02775387_v8_n17_p2091_Tokman |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
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R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| description |
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. |
| format |
JOUR |
| author |
Tokman, A.L. Gentil, L.A. Olabe, J.A. |
| spellingShingle |
Tokman, A.L. Gentil, L.A. Olabe, J.A. Substitution kinetics in the complexes of pentacyanoruthenate(II) with ethylenediamine |
| author_facet |
Tokman, A.L. Gentil, L.A. Olabe, J.A. |
| author_sort |
Tokman, A.L. |
| title |
Substitution kinetics in the complexes of pentacyanoruthenate(II) with ethylenediamine |
| title_short |
Substitution kinetics in the complexes of pentacyanoruthenate(II) with ethylenediamine |
| title_full |
Substitution kinetics in the complexes of pentacyanoruthenate(II) with ethylenediamine |
| title_fullStr |
Substitution kinetics in the complexes of pentacyanoruthenate(II) with ethylenediamine |
| title_full_unstemmed |
Substitution kinetics in the complexes of pentacyanoruthenate(II) with ethylenediamine |
| title_sort |
substitution kinetics in the complexes of pentacyanoruthenate(ii) with ethylenediamine |
| url |
http://hdl.handle.net/20.500.12110/paper_02775387_v8_n17_p2091_Tokman |
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1807323591400751104 |