Artículo
Abstract:
The mixed-valence ion, [(NH3)5RuIII-NC-OsII(CN)5]-, was prepared in solution from [Ru(NH3)5H2O]3+ and [Os(CN)6]4- and was isolated as a potassium salt. A kinetic study of the formation reaction shows that a dissociative mechanism is operative, the process being rate-controlled by the loss of water from the Ru(III) moiety, as in related reactions with [Fe(CN)6]4- and [Ru(CN)6]4-. The binuclear ion shows a distinctive intervalence band, associated to charge transfer from Os(II) to Ru(III), at 830 nm (ε{lunate}=3450 M-1 cm-1), with a noticeable asymmetry, probably associated to spin-orbit coupling. Shifts in the redox potentials at the metal centers on dimer formation are consistent with the Os(II)-Ru(III) formulation. By measuring solution Raman spectra in post-resonance conditions with respect to the IT band, activation of the bridging CN stretching, as well as of the terminal stretching modes, is observed; absolute distortion values for both of the modes can be calculated by applying a time-dependent analysis of the scattering problem. IR and Raman results of the solid samples are also presented. Theoretical models were applied to IT data, allowing an estimation of the delocalization parameter, α2, and the electronic coupling parameter, HAB. The results are compared with other valence-trapped binuclear systems. © 1994.
Registro:
| Documento: | Artículo |
| Título: | Properties of the mixed-valence binuclear complex ion, (NH3)5RuIII-NC-OsII(CN)5]- |
| Autor: | Forlano, P.; Baraldo, L.M.; Olabe, J.A.; Della Védova, C.O. |
| Filiación: | Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Capital Federal, Argentina Programa QUINOR (Conicet), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115, 1900 La Plata, Argentina |
| Palabras clave: | Ammine complexes; Cyano complexes; Mixed-valence complexes; Osmium complexes; Ruthenium complexes |
| Año: | 1994 |
| Volumen: | 223 |
| Número: | 1-2 |
| Página de inicio: | 37 |
| Página de fin: | 42 |
| DOI: | http://dx.doi.org/10.1016/0020-1693(94)03987-9 |
| Título revista: | Inorganica Chimica Acta |
| Título revista abreviado: | Inorg. Chim. Acta |
| ISSN: | 00201693 |
| CODEN: | ICHAA |
| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201693_v223_n1-2_p37_Forlano |
Referencias:
- Creutz, (1983) Prog. Inorg. Chem., 30, p. 1
- Olabe, Haim, (1989) Inorg. Chem., 28, p. 3277
- Yeh, Haim, (1985) Journal of the American Chemical Society, 107, p. 36
- Hwang, Chen, Yang, Yeh, (1991) Inorganic Chemistry, 30, p. 1862
- Siddiqui, Henderson, Shepherd, (1987) Inorg. Chem., 26, p. 3101
- Burewicz, Haim, (1988) Inorganic Chemistry, 27, p. 1611
- Schoonover, Timpson, Meyer, Bignozzi, (1992) Inorg. Chem., 31, p. 3185
- Bignozzi, Argazzi, Schoonover, Gordon, Dyer, Scandola, (1992) Inorg. Chem., 31, p. 5260
- Bignozzi, Argazzi, Chiorboli, Raffia, Scandola, (1991) Coord. Chem. Rev., 11, p. 261
- Bignozzi, Raffia, Scandola, (1985) J. Am. Chem. Soc., 107, p. 1644
- Bignozzi, Paradisi, Raffia, Scandola, (1988) Inorg. Chem., 27, p. 408
- Scandola, Argazzi, Bignozzi, Chiorboli, Indelli, Rampi, (1993) Coord. Chem. Rev., 125, p. 283
- Ludi, (1971) Chimia, 26, p. 647
- L.M. Baraldo, M.S. Bessega, G.E. Rigotti and J.A. Olabe, submitted for publication; Vogt, Jr., Katz, Wiberley, (1965) Inorg. Chem., 4, p. 1157
- Dixon, Lawrance, Lay, Sargeson, (1984) Inorg. Chem., 23, p. 2940
- Krause, Violette, (1986) Inorg. Chim. Acta, 113, p. 161
- Alexander, Gray, (1968) J. Am. Chem. Soc., 90, p. 4260
- Gentil, Navaza, Olabe, Rigotti, (1991) Inorg. Chim. Acta, 179, p. 89
- Curtis, Meyer, (1982) Inorg. Chem., 21, p. 1562
- Kuehn, Taube, (1976) J. Am. Chem. Soc., 98, p. 689
- Macartney, (1991) Inorg. Chem., 30, p. 3337
- Taube, (1981) Comments on Inorganic Chemistry, 1, p. 17
- Hester, Nour, (1981) Journal of the Chemical Society, Dalton Transactions, p. 939
- Walker, Barbara, Doorn, Dong, Hupp, (1991) J. Phys. Chem., 95, p. 5712
- Doorn, Hupp, (1989) J. Am. Chem. Soc., 111, p. 1142
- Heller, Sundberg, Tannor, (1982) J. Phys. Chem., 86, p. 1822
- Tannor, Heller, (1982) J. Chem. Phys., 77, p. 202
- Lee, Heller, (1977) The Journal of Chemical Physics, 71, p. 4777
- Heller, (1981) Acc. Chem. Res., 14, p. 368
- Vogler, Osman, Kunkely, (1987) Inorg. Chem., 26, p. 2337
- Kober, Goldsby, Narayana, Meyer, (1983) J. Am. Chem. Soc., 105, p. 4303
Citas:
---------- APA ----------
Forlano, P., Baraldo, L.M., Olabe, J.A. & Della Védova, C.O. (1994) . Properties of the mixed-valence binuclear complex ion, (NH3)5RuIII-NC-OsII(CN)5]-. Inorganica Chimica Acta, 223(1-2), 37-42.http://dx.doi.org/10.1016/0020-1693(94)03987-9
---------- CHICAGO ----------
Forlano, P., Baraldo, L.M., Olabe, J.A., Della Védova, C.O. "Properties of the mixed-valence binuclear complex ion, (NH3)5RuIII-NC-OsII(CN)5]-" . Inorganica Chimica Acta 223, no. 1-2 (1994) : 37-42.http://dx.doi.org/10.1016/0020-1693(94)03987-9
---------- MLA ----------
Forlano, P., Baraldo, L.M., Olabe, J.A., Della Védova, C.O. "Properties of the mixed-valence binuclear complex ion, (NH3)5RuIII-NC-OsII(CN)5]-" . Inorganica Chimica Acta, vol. 223, no. 1-2, 1994, pp. 37-42.http://dx.doi.org/10.1016/0020-1693(94)03987-9
---------- VANCOUVER ----------
Forlano, P., Baraldo, L.M., Olabe, J.A., Della Védova, C.O. Properties of the mixed-valence binuclear complex ion, (NH3)5RuIII-NC-OsII(CN)5]-. Inorg. Chim. Acta. 1994;223(1-2):37-42.http://dx.doi.org/10.1016/0020-1693(94)03987-9
