Artículo
Scheiring, T.; Kaim, W.; Olabe, J.A.; Parise, A.R.; Fiedler, J. "The valence-localized decacyanodiruthenium(III,II) analogue of the Creutz-Taube ion. Completing the full d5/d6 triad [(NC)5M(μ-pz)M(CN)5]5-, M = Fe,Ru,Os; pz = pyrazine" (2000) Inorganica Chimica Acta. 300-302:125-130
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Abstract:
The new ruthenium(II) complex ion [(NC)5Ru(μ-pz)Ru(CN)5]6- has been prepared and studied as the hexakis(tetraethylammonium) salt. Although spectroelectrochemical experiments in dichloromethane were affected by adsorption as they were in other solvents, the compound could be oxidized via two reversible one-electron steps with a mixed-valent pentaanionic intermediate. In comparison with the iron and osmium analogues, the system [(NC)5Ru(μ-pz)Ru(CN)5]5- is distinguished by less negative redox potentials, a smaller comproportionation constant K(c) of only 104.7, a very broad (Δv( 1/2 ) = 4200 cm-1) symmetrical IVCT band at 1760 nm (ε = 2600 M-1 cm-1) conforming with the Hush model for weakly coupled mixed-valent systems, the absence of an EPR signal even at 3.5 K and the appearance of infrared bands (CN, pyrazine ring vibrations) indicating localized valence on the time scale of 10-12 s. Together with the high MLCT energies these results suggest a weaker metal-pyrazine interaction for the ruthenium system in comparison with the Fe and Os analogues reported previously. In relation to the Creutz-Taube ion, the substitution of ammine ligands by non-innocent cyanide ions attenuates the metal-metal interaction across the π accepting pyrazine bridge. (C) 2000 Elsevier Science S.A.
Registro:
| Documento: | Artículo |
| Título: | The valence-localized decacyanodiruthenium(III,II) analogue of the Creutz-Taube ion. Completing the full d5/d6 triad [(NC)5M(μ-pz)M(CN)5]5-, M = Fe,Ru,Os; pz = pyrazine |
| Autor: | Scheiring, T.; Kaim, W.; Olabe, J.A.; Parise, A.R.; Fiedler, J. |
| Filiación: | Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Ciudad Universitaria, Buenos Aires 1428, Argentina J. Heyrovsky Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejškova 3, CZ-18223 Prague, Czech Republic |
| Palabras clave: | Cyano complexes; Mixed-valence complexes; Ruthenium complexes; Spectroelectrochemistry; pyrazine derivative; ruthenium derivative; article; complex formation; Czech Republic; electrochemistry; Germany; molecular interaction; oxidation reduction reaction |
| Año: | 2000 |
| Volumen: | 300-302 |
| Página de inicio: | 125 |
| Página de fin: | 130 |
| DOI: | http://dx.doi.org/10.1016/S0020-1693(99)00456-9 |
| 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_v300-302_n_p125_Scheiring |
Referencias:
- Shriver, D.F., Atkins, P.W., Langford, C.H., (1994), p. 611. , Inorganic Chemistry, second ed., Oxford University Press, Oxford; Cotton, F.A., Wilkinson, G., Murillo, C.A., Bochmann, M., (1999), p. 1017. , Advanced Inorganic Chemistry, sixth ed., Wiley, New York; Bersuker, I.B., (1996), p. 531. , Electronic Structure and Properties of Transition Metal Compounds, Wiley, New York; Prassides, K., (1991), Mixed Valency Systems: Applications in Chemistry, Physics and Biology, NATO ASI Series, Kluwer, Dordrecht; Crutchley, R.J., (1994) Adv. Inorg. Chem., 41, p. 273
- Creutz, C., (1983) Prog. Inorg. Chem., 30, p. 1
- Felix, F., Hauser, U., Siegenthaler, H., Wenk, F., Ludi, A., (1975) Inorg. Chim. Acta, 15, pp. L7
- Felix, F., Ludi, A., (1978) Inorg. Chem., 17, p. 1782
- Moore, K.J., Lee, L., Mabbott, G.A., Petersen, J.D., (1983) Inorg. Chem., 22, p. 1108
- Ketterle, M., Kaim, W., Olabe, J.A., Parise, J.R., Fiedler, J., (1999) Inorg. Chim. Acta, 291, p. 66
- Creutz, C., Chou, M.H., (1987) Inorg. Chem., 26, p. 2995
- Hornung, F., Baumann, F., Kaim, W., Olabe, J.A., Slep, L.D., Fiedler, J., (1998) Inorg. Chem., 37, p. 311. , 5402
- Waldhor, E., Kaim, W., Olabe, J.A., Slep, L.D., Fiedler, J., (1997) Inorg. Chem., 36, p. 2969
- Krejcik, M., Danek, M., Hartl, F., (1991) J. Electroanal. Chem. Interfac. Electrochem., 317, p. 179
- Kaim, W., Ernst, S., Kasack, V., (1990) J. Am. Chem. Soc., 112, p. 173
- Kaim, W., Ernst, S., Kasack, V., (1990) J. Am. Chem. Soc., 112, p. 173
- Toma, H.E., Takasugi, M.S., (1989) Polyhedron, 8, p. 941
- Timpson, C.J., Bignozzi, C.A., Sullivan, B.P., Kober, E.M., Meyer, T.J., (1996) J. Phys. Chem., 100, p. 2915
- Thoma, H.E., Takasugi, M.S., (1983) J. Soln. Chem., 12, p. 547
- Mayer, U., Gutmann, V., Gerger, W., (1975) Monatsh. Chem., 106, p. 1235
- Robin, M.B., Day, P., (1967) Adv. Inorg. Chem. Radiochem., 10, p. 247
- Best, S.P., Clark, R.J.H., McQueen, R.C.S., Joss, S., (1989) J. Am. Chem. Soc., 111, p. 548
- Crean, F.M., Schug, K., (1984) Inorg. Chem., 23, p. 853
- Kang, H.W., Moran, G., Krausz, E., (1996) Inorg. Chim. Acta, 249, p. 231
- Lay, P.A., Magnuson, R.H., Taube, H., (1988) Inorg. Chem., 27, p. 2364
- Richardson, D.E., Taube, H., (1983) J. Am. Chem. Soc., 105, p. 40
- Lever, A.B.P., (1984), Inorganic Electronic Spectroscopy, second. ed., Elsevier, Amsterdam; Allen, G.C., Hush, N.S., (1967) Prog. Inorg. Chem., 8, p. 357
- Hush, N.S., (1967) Prog. Inorg. Chem., 8, p. 391
- Kasack, V., Kaim, W., Binder, H., Jordanov, J., Roth, E., (1995) Inorg. Chem., 34, p. 1924
- Demadis, K.D., Neyhart, G.A., Kober, E.M., Meyer, T.J., (1998) J. Am. Chem. Soc., 120, p. 7121
- Slep, L.D., Pollak, S., Olabe, J.A., (1999) Inorg. Chem., 38, p. 4369
- Glockle, M., Kaim, W., Fiedler, J., (1998) Organometallics, 17, p. 4923
Citas:
---------- APA ----------
Scheiring, T., Kaim, W., Olabe, J.A., Parise, A.R. & Fiedler, J. (2000) . The valence-localized decacyanodiruthenium(III,II) analogue of the Creutz-Taube ion. Completing the full d5/d6 triad [(NC)5M(μ-pz)M(CN)5]5-, M = Fe,Ru,Os; pz = pyrazine. Inorganica Chimica Acta, 300-302, 125-130.http://dx.doi.org/10.1016/S0020-1693(99)00456-9
---------- CHICAGO ----------
Scheiring, T., Kaim, W., Olabe, J.A., Parise, A.R., Fiedler, J. "The valence-localized decacyanodiruthenium(III,II) analogue of the Creutz-Taube ion. Completing the full d5/d6 triad [(NC)5M(μ-pz)M(CN)5]5-, M = Fe,Ru,Os; pz = pyrazine" . Inorganica Chimica Acta 300-302 (2000) : 125-130.http://dx.doi.org/10.1016/S0020-1693(99)00456-9
---------- MLA ----------
Scheiring, T., Kaim, W., Olabe, J.A., Parise, A.R., Fiedler, J. "The valence-localized decacyanodiruthenium(III,II) analogue of the Creutz-Taube ion. Completing the full d5/d6 triad [(NC)5M(μ-pz)M(CN)5]5-, M = Fe,Ru,Os; pz = pyrazine" . Inorganica Chimica Acta, vol. 300-302, 2000, pp. 125-130.http://dx.doi.org/10.1016/S0020-1693(99)00456-9
---------- VANCOUVER ----------
Scheiring, T., Kaim, W., Olabe, J.A., Parise, A.R., Fiedler, J. The valence-localized decacyanodiruthenium(III,II) analogue of the Creutz-Taube ion. Completing the full d5/d6 triad [(NC)5M(μ-pz)M(CN)5]5-, M = Fe,Ru,Os; pz = pyrazine. Inorg. Chim. Acta. 2000;300-302:125-130.http://dx.doi.org/10.1016/S0020-1693(99)00456-9
