Artículo
Waldhör, E.; Kaim, W.; Olabe, J.A.; Slep, L.D.; Fiedler, J. "The mpz+/mpz. Pair as Organic Analogue of the NO+/NO. Ligand Redox System (mpz = N-Methylpyrazinium). A Combined Electrochemical and Spectroscopic Study (UV/Vis/NIR, IR, EPR) of Complexes [(mpz)M(CN)5]2-/3- (M = Fe, Ru, Os)" (1997) Inorganic Chemistry. 36(14):2969-2974
Consulte la política de Acceso Abierto del editor
Abstract:
The oxidation and reduction behavior of complexes [(mpz)M(CN)5]2- between the group 8 pentacyanometalates-(II) and the N-methylpyrazinium ion mpz+ was studied using spectroelectrochemical techniques (UV/vis/NIR, IR, EPR) in nonaqueous and, in part, aqueous media. As a further source of information on the electronic structure, we studied the variable solvatochromism of MLCT absorption bands in the precursor ions [(mpz)M(CN)5]2- The mpz-centered one-electron reduction showed a tendency for concomitant loss of cyanide (EC process) to yield ions [(mpz)M(CN)4]2-, the lability increasing in the order M = Os < < Ru < Fe. In contrast to the EPR spectra obtained from reduction with S2O4 2- in aqueous media, which showed no evidence for close mpz. /metal association, the intra muros electrolysis experiments in DMSO or acetonitrile yielded the following results: The EPR spectrum that was previously assigned to [(mpz)Fe(CN)5]3- is now ascribed to [(mpz)Fe(CN4)]2-. Whereas the dissociatively inert osmium radical complex [(mpz)Os(CN)5]3- is distinguished by a broad EPR signal with a rather large value gisa = 2.0157, the EPR spectrum of [(mpz)Ru(CN)4]3- reveals well-resolved separate coupling with the 99Ru and 101Ru isotopes in natural abundance. Spectroelectrochemistry and reactivity patterns of the complex ions [(mpz)M(CN)5]2- are reminiscent of results for corresponding nitrosyl complexes [(NO)M(CN)5]2-, which suggests that the mpz+/mpz. ligand redox pair can function as an organic analogue of the NO+/NO. redox system.
Registro:
| Documento: | Artículo |
| Título: | The mpz+/mpz. Pair as Organic Analogue of the NO+/NO. Ligand Redox System (mpz = N-Methylpyrazinium). A Combined Electrochemical and Spectroscopic Study (UV/Vis/NIR, IR, EPR) of Complexes [(mpz)M(CN)5]2-/3- (M = Fe, Ru, Os) |
| Autor: | Waldhör, E.; Kaim, W.; Olabe, J.A.; Slep, L.D.; Fiedler, J. |
| Filiación: | Inst. für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany Departarnento de Quim. Inorg., Fac. de Ciencias Exactas y Naturales, Ciudad Universitaria, Buenos Aires, Capital Federal 1428, Argentina J. Heyrovsky Inst. of Phys. Chem., Acad. of Sci. of the Czech Republic, Dolejškova 3, CZ-182 23 Prague 8, Czech Republic |
| Año: | 1997 |
| Volumen: | 36 |
| Número: | 14 |
| Página de inicio: | 2969 |
| Página de fin: | 2974 |
| Título revista: | Inorganic Chemistry |
| Título revista abreviado: | Inorg. Chem. |
| ISSN: | 00201669 |
| CODEN: | INOCA |
| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v36_n14_p2969_Waldhor |
Referencias:
- McCleverty, J.A., (1979) Chem. Rev., 79, p. 37
- Clarke, M.J., Gaul, J.B., (1993) Struct, Bonding (Berlin), 81, p. 147
- Feltham, R.D., Enemark, J.M., (1981) Top, Stereochem., 12, p. 155
- Darby, W.L., Vallarino, L.M., (1983) Inorg. Chim. Acta, 75, p. 65. , and literature cited
- Bruns, W., Hausen, H.-D., Kaim, W., Schulz, A., (1993) J. Organomet. Chem., 444, p. 121
- Hilgers, F., Bruns, W., Fiedler, J., Kaim, W., (1996) J. Organnmet. Chem., 551, p. 273
- Kaim, W., Matheis, W., (1990) Chem. Ber., 123, p. 1323
- Matheis, W., Kaim, W., (1990) J. Chem. Soc., Faraday Trans., 86, p. 3337
- Inoue, M.B., Inoue, M., Bruck, M.A., Fernando, Q., (1992) J. Chem. Soc., Chem. Commun., p. 515
- Stamler, J.S., Singel, D.J., Loscalzo, J., (1992) Science, 258, p. 1898
- Butler, A.R., Williams, D.L.H., (1993) Chem. Soc. Rev., p. 233
- Toma, H.E., Malin, J.M., (1973) Inorg. Chem., 12, p. 1039
- Wohlers, H.D., Tassel, K.D., Bowermann, B.A., Petersen, J.D., (1980) Inorg. Chem., 19, p. 2837
- Eaton, D.R., Watkins, J.M., Buist, R.J., (1985) J. Am. Chem. Soc., 107, p. 5604
- Ford, P.D., Rudd, D.P., Gaunder, R., Taube, H., (1968) J. Am. Chem. Soc., 90, p. 1187
- Creutz, C., Chou, M.H., (1987) Inorg. Chem., 26, p. 2995
- Wishart, J.F., Bino, A., Taube, H., (1986) Inorg. Chem., 25, p. 3318
- Poppe, J., Kaim, W., Ben Altabef, A., Katz, N.E., (1993) J. Chem. Soc., Perkin Trans. 2, p. 2105
- Johnson, C.R., Shepherd, R.E., (1983) Inorg. Chem., 22, p. 1117
- Johnson, C.R., Shepherd, R.E., (1983) Inorg. Chem., 22, p. 2439
- Hoddenbagh, J.M.A., Macartney, D.H., (1986) Inorg. Chem., 25, p. 2099
- Hoddenbagh, J.M.A., Macartney, D.H., (1986) Inorg. Chem., 25, p. 380
- Slep, L.D., Baraldo, L.M., Olabe, J.A., (1996) Inorg. Chem., 35, p. 6327
- Rakowsky, T., Dohrmann, J.K., (1979) Ber, Bumenges, Phys. Chem., 83, p. 495
- Kaim, W., (1987) Coord, Chem. Rev., 76, p. 187
- Bard, A.J., Parsons, R., Jordan, J., (1985) Standard Potentials in Aqueous Solutions, , IUPAC: Oxford, U.K
- Krejcik, M., Danek, M., Hartl, F., (1991) J. Electroanal. Chem. Interfacial Electrochem., 317, p. 179
- Kaim, W., Ernst, S., Kasack, V., (1990) J. Am. Chem. Soc., 112, p. 173
- Bowden, W.L., Bonnar, P., Brown, D.B., Geiger, W.E., (1977) Inorg. Chem., 16, p. 41
- Fiedler, J., (1993) Coll. Czech. Chem. Commun., 58, p. 461
- Fiedler, J., Masek, J., (1986) Inorg. Chim. Acta, 111, p. 39
- Masek, J., Maslova, E., (1974) Coll. Czech. Chem. Commun., 39, p. 2141
- Ernst, S., Kaim, W., (1986) J. Am. Chem. Soc., 108, p. 3578
- Manoharan, P.T., Gray, H.B., (1965) J. Am. Chem. Soc., 87, p. 3340
- Olabe, J.A., Gentil, L.A., Rigotti, G., Navaza, A., (1984) Inorg. Chem., 23, p. 4297
- Baraldo, L.M., Bessega, M.S., Rigotti, G.E., Olabe, J.A., (1994) Inorg. Chem., 33, p. 5890
- Darensbourg, D.J., Klausmeyer, K.K., Mueller, B.L., Reibenspies, J.H., (1992) Angew. Chem., 104, p. 1501
- (1992) Angew. Chem., Int. Ed. Engl., 31, p. 1503
- Hartl, F., Vlcek Jr., A., DeLearie, L.A., Pierpont, C.G., (1990) Inorg. Chem., 29, p. 1073
- Kaim, W., (1987) Rev. Chem. Intermed., 8, p. 247
- Kaim, W., Schulz, A., Hilgers, F., Hausen, H.-D., Moscherosch, M., Lichtblau, A., Jordanov, J., Zalis, S., (1993) Rev. Chem. Intermed., 19, p. 603
- Kaim, W., Bruns, W., Kohlmann, S., Kiejcik, M., (1995) Inorg. Chim. Acta, 229, p. 143
- Atwood, C.G., Geiger, W.E., (1993) J. Am. Chem. Soc., 115, p. 5310
- Kober, E.M., Meyer, T.J., (1982) Inorg. Chem., 21, p. 3966
- Johnson, S.R., Westmorland, T.D., Caspar, J.V., Barqawi, K.R., (1988) Inorg. Chem., 27, p. 3195
- Lay, P.A., Magnuson, R.H., Taube, H., (1988) Inorg. Chem., 27, p. 2364
- Reichardi, C., (1988) Solvent and Solvent Effects in Organic Chemistry, 2nd. Ed., , Verlag Chemie: Weinheim, Germany
- Gutmann, V., Resch, G., Linert, W., (1982) Coord, Chem. Rev., 43, p. 133
- Goodman, B.A., Raynor, J.B., (1970) Adv. Inorg. Chem. Radiochem., 13, p. 135
- Weil, J.A., Bolton, J.R., Wertz, J.E., (1994) Electron Paramagnetic Resonance, , Wiley: New York
- Waldhör, E., Poppe, J., Kaim, W., Cutin, E.H., Garcia Posse, M., Katz, N.E., (1995) Inorg. Chem., 34, p. 3093
- Samuels, A.C., DeArmond, M.K., (1995) Inorg. Chem., 34, p. 5548
- Kaim, W., (1984) J. Chem. Soc. Perkin Trans. 2, p. 1357
Citas:
---------- APA ----------
Waldhör, E., Kaim, W., Olabe, J.A., Slep, L.D. & Fiedler, J. (1997) . The mpz+/mpz. Pair as Organic Analogue of the NO+/NO. Ligand Redox System (mpz = N-Methylpyrazinium). A Combined Electrochemical and Spectroscopic Study (UV/Vis/NIR, IR, EPR) of Complexes [(mpz)M(CN)5]2-/3- (M = Fe, Ru, Os). Inorganic Chemistry, 36(14), 2969-2974.Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v36_n14_p2969_Waldhor [ ]
---------- CHICAGO ----------
Waldhör, E., Kaim, W., Olabe, J.A., Slep, L.D., Fiedler, J. "The mpz+/mpz. Pair as Organic Analogue of the NO+/NO. Ligand Redox System (mpz = N-Methylpyrazinium). A Combined Electrochemical and Spectroscopic Study (UV/Vis/NIR, IR, EPR) of Complexes [(mpz)M(CN)5]2-/3- (M = Fe, Ru, Os)" . Inorganic Chemistry 36, no. 14 (1997) : 2969-2974.Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v36_n14_p2969_Waldhor [ ]
---------- MLA ----------
Waldhör, E., Kaim, W., Olabe, J.A., Slep, L.D., Fiedler, J. "The mpz+/mpz. Pair as Organic Analogue of the NO+/NO. Ligand Redox System (mpz = N-Methylpyrazinium). A Combined Electrochemical and Spectroscopic Study (UV/Vis/NIR, IR, EPR) of Complexes [(mpz)M(CN)5]2-/3- (M = Fe, Ru, Os)" . Inorganic Chemistry, vol. 36, no. 14, 1997, pp. 2969-2974.Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v36_n14_p2969_Waldhor [ ]
---------- VANCOUVER ----------
Waldhör, E., Kaim, W., Olabe, J.A., Slep, L.D., Fiedler, J. The mpz+/mpz. Pair as Organic Analogue of the NO+/NO. Ligand Redox System (mpz = N-Methylpyrazinium). A Combined Electrochemical and Spectroscopic Study (UV/Vis/NIR, IR, EPR) of Complexes [(mpz)M(CN)5]2-/3- (M = Fe, Ru, Os). Inorg. Chem. 1997;36(14):2969-2974.Available from: https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v36_n14_p2969_Waldhor [ ]
