Artículo
Abstract:
The nucleophilic addition of OH- to [Ru(CN)5(NO)]2- leads to the N-bonded pentacyanonitroruthenate(II) ion (λmax = 320 nm, ε = 3850 dm3 mol-1 cm-1). The stoichiometry is 2:1 ([OH-]:[Ru]) and the equilibrium formation constant is 4.4 × 106 dm6 mol-2 (25 °C, I = 1 mol dm-3). A kinetic study of the forward reaction showed that it is first order in the concentration of each reactant, with k = 0.95 dm3 mol-1 s-1 (25 °C, I = 1 mol dm-3), ΔH‡ = 57.3 ± 3.3 kJ mol-1 and ΔS‡ = -54.0 ± 4.5 J K-1 mol-1. The mechanism involves two consecutive attacks by OH-, the first being rate determining. The reaction product decays by an aquation process, leading to [Ru(CN)5(H2O)]3- and free NO2 -. The rate constant for the dissociation reaction of [Ru(CN)5(NO2)]4- is k-N = 2.00 × 10-4 s-1 (25 °C, I = 1 mol dm-3). In the formation reaction, both nitrite (O-bound) and nitro (N-bound) linkage isomers are formed, with kO and kN being 0.23 and 0.15 dm3 mol-1 s-1 respectively (25 °C, I = 1 mol dm-3). The O-bound isomer isomerizes slowly to the thermodynamically more stable N-bound isomer. The kinetic and thermodynamic parameters have been analysed by comparison with the chemistry of the complexes [Fe(CN)5(NO)]2- and [Fe(CN)5(NO2)]4-.
Registro:
| Documento: | Artículo |
| Título: | Nitrosyl-nitrite interconversion in pentacyanoruthenate(II) complexes |
| Autor: | Chevalier, A.A.; Gentil, L.A.; Olabe, J.A. |
| Filiación: | Departamento de Química, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Mar del Plata, 7600 Mar del Plata, Argentina Departamento de Ingeniería Química, Facultad de Ingeniería, Universidad Nacional de Mar del Plata, 7600 Mar del Plata, Argentina Departamento de Quimica Inorganica, Analitica y Quimica Fisica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Capital Federal, Argentina |
| Año: | 1991 |
| Número: | 8 |
| Página de inicio: | 1959 |
| Página de fin: | 1963 |
| DOI: | http://dx.doi.org/10.1039/DT9910001959 |
| Título revista: | Journal of the Chemical Society, Dalton Transactions |
| ISSN: | 14727773 |
| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14727773_v_n8_p1959_Chevalier |
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Citas:
---------- APA ----------
Chevalier, A.A., Gentil, L.A. & Olabe, J.A. (1991) . Nitrosyl-nitrite interconversion in pentacyanoruthenate(II) complexes. Journal of the Chemical Society, Dalton Transactions(8), 1959-1963.http://dx.doi.org/10.1039/DT9910001959
---------- CHICAGO ----------
Chevalier, A.A., Gentil, L.A., Olabe, J.A. "Nitrosyl-nitrite interconversion in pentacyanoruthenate(II) complexes" . Journal of the Chemical Society, Dalton Transactions, no. 8 (1991) : 1959-1963.http://dx.doi.org/10.1039/DT9910001959
---------- MLA ----------
Chevalier, A.A., Gentil, L.A., Olabe, J.A. "Nitrosyl-nitrite interconversion in pentacyanoruthenate(II) complexes" . Journal of the Chemical Society, Dalton Transactions, no. 8, 1991, pp. 1959-1963.http://dx.doi.org/10.1039/DT9910001959
---------- VANCOUVER ----------
Chevalier, A.A., Gentil, L.A., Olabe, J.A. Nitrosyl-nitrite interconversion in pentacyanoruthenate(II) complexes. 1991(8):1959-1963.http://dx.doi.org/10.1039/DT9910001959
