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Abstract:

The pyrazine-bridged diosmium(II) complex {(μ-C4H4N2)[Os(CN)5] 2}6- has been synthesized as the hexapotassium salt and was converted to the hexakis(tetrabutylammonium) compound by ion exchange. Its stepwise oxidation to the Os2IIIOsII and Os2IIIOsIII states was monitored spectroelectrochemically in acetonitrile/0.1 M Bu4NPF6 in the UV-vis-NIR and IR regions and by EPR. The OsII2 species exhibits long-wavelength solvatochromic MLCT bands at 14 800 and 18 480 cm-1. The pentaanionic mixed-valent ion has a comproportionation constant Kc of 105.8 and is distinguished by several electronic absorptions in the IR region. The bands at 1972, 2480, 4000, 5000, 7170, and 11 900 cm-1 are similar but appreciably lower in energy than those reported for the analogous complex {(μ-C4H4N2)[Os(NH3) 5]2}5+. In addition to CN vibrational stretching features shifted on electron transfer there is an additional sharp band only for the 5- ion at 1582 cm-1 which is attributed to a pyrazine ring vibration. The intensity of this band suggests an unsymmetrical situation and thus valence localization on the vibrational time scale. The EPR signals at g⊥ = 2.0563 and gpar; = 1.761 point toward excited states lying close to the doublet ground state and to significant metal/cyanide interaction. Compared to the Creutz-Taube ion {(μ-C4H4N2)[Ru-(NH3) 5]2}5+ and its osmium homologue, the 5- ion described here exhibits a lower degree of metal-metal coupling.

Registro:

Documento: Artículo
Título:Spectroelectrochemical Characterization of the Two-Step Redox System {(μ-pz)[Os(CN)5]2}n- (n = 4, 5, 6; pz = Pyrazine). Similarities and Differences in Relation to the Creutz-Taube System
Autor:Hornung, F.M.; Baumann, F.; Kaim, W.; Olabe, J.A.; Slep, L.D.; Fiedler, J.
Filiación:Inst. für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany
Depto. de Quim. Inorgánica, Fac. de Cie. Exactas/Naturales, UBA, Pabellón 2, Cd. Universitaria, Buenos Aires, Capital Federal 1428, Argentina
J. Heyrovsky Inst. of Phys. Chem., Acad. of Sciences of Czech Republic, Dolejškova 3, CZ-18223 Prague, Czech Republic
Año:1998
Volumen:37
Número:2
Página de inicio:311
Página de fin:316
Título revista:Inorganic Chemistry
Título revista abreviado:Inorg. Chem.
ISSN:00201669
CODEN:INOCA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v37_n2_p311_Hornung

Referencias:

  • Prassides, K., (1991) Mixed Valency Systems-Applications in Chemistry, Physics and Biology, , Kluwer Academic Publishers: Dordrecht, The Netherlands
  • Creutz, C., (1983) Prog. Inorg. Chem., 30, p. 1
  • Crutchley, R.J., (1994) Adv. Inorg. Chem., 41, p. 273
  • Richardson, D.E., Taube, H., (1984) Coord. Chem. Rev., 60, p. 107
  • Kaim, W., Bruns, W., Poppe, J., Kasack, V., (1993) J. Mol. Struct., 292, p. 221
  • Ward, M.D., (1995) Chem. Soc. Rev., 34, p. 121
  • Taube, H., (1978) Ann. N. Y. Acad. Sci., 313, p. 481
  • Broo, A., Lincoln, P., (1997) Inorg. Chem., 36, p. 2544
  • Creutz, C., Taube, H., (1969) J. Am. Chem. Soc., 91, p. 3988
  • Creutz, C., Taube, H., (1973) J. Am. Chem. Soc., 95, p. 1086
  • Lay, P.A., Magnuson, R.H., Taube, H., (1988) Inorg. Chem, 27, p. 2364
  • 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
  • Larèze, F.C., (1976) R. Seances Acad. Sci., Ser. C, 282, p. 737
  • (1976) Chem. Abstr., 85, pp. 28051w
  • Gross, R., Kaim, W., (1986) Inorg. Chem, 25, p. 498
  • Bruns, W., Kaim, W., Waldhör, E., Krejcik, M., (1993) J. Chem. Soc., Chem, Commun., p. 1868
  • Bruns, W., Kaim, W., Waldhör, E., Krejcik, M., (1995) Inorg. Chem, 34, p. 663
  • Tom, G.M., Creutz, C., Taube, H., (1974) J. Am. Chem. Soc., 96, p. 7828
  • Nemzek, M.A., Callahan, R.W., (1980) J. Chem. Soc., Chem. Commun., p. 1231
  • Kaim, W., Kasack, V., (1990) Inorg. Chem., 29, p. 4696
  • Kasack, V., Kaim, W., Binder, H., Jordanov, J., Ruth, E., (1995) Inorg. Chem, 34, p. 1924
  • Naklicki, M.L., White, C.A., Kondratiev, V.V., Crutchley, R.J., (1996) Inorg. Chim. Acta, 242, p. 63
  • Ribou, A.-C., Launay, J.-P., Taktihashi, K., Nihira, T., Tarutani, S., Spangler, C.W., (1994) Inorg. Chem., 33, p. 1325
  • Ribou, A.-C., Launay, J.-P., Sachtleben, M.L., Li, H., Spangler, C.W., (1996) Inorg. Chem., 35, p. 3735
  • Cargill Thompson, A.M.W., Gatteschi, D., McCleverty, J.A., Navas, J.A., Rentschler, E., Ward, M.D., (1996) Inorg. Chem., 55, p. 2701
  • Ernst, S., Kasack, V., Kaim, W., (1988) Inorg. Chem., 27, p. 1146
  • Richardson, D.E., Taube, H., (1983) J. Am.Chem. Soc., 105, p. 40
  • Wiodarczyk, A., Maher, J.P., McCleverty, J.A., Ward, M.D., (1995) J. Chem. Soc., Chem. Commun., p. 2397
  • Puppe, J., Moscherosch, M., Kaim, W., (1993) Inorg. Chem., 32, p. 2640
  • Kaim, W., Bruns, W., Kohlmann, S., Krejcik, M., (1995) Inorg. Chim. Acta, 229, p. 143
  • Beley, M., Collin, J.-P., Louis, R., Metz, B., Sauvage, J.-P., (1991) J. Am. Chem. Soc., 113, p. 8521
  • Sutter, J.-P., Grove, D.M., Beley, M., Collin, J.-P., Veldman, N., Spek, A.L., Sauvage, J.-P., Van Koten, G., (1994) Angew. Chem., Int. Ed. Engl., 33, p. 1282
  • Beley, M., Chodorowski-Kimmes, S., Collin, J.-P., Lainé, P., Launay, J.-P., Sauvage, J.-P., (1994) Angew. Chem., Int. Ed. Engl., 33, p. 1775
  • Spreer, L.O., Allan, C.B., MacQueen, D.B., Otvos, J.W., Calvin, M., (1994) J. Am. Chem. Soc., 116, p. 2187
  • Moscherosch, M., Waldhör, E., Binder, H., Kaim, W., Fiedler, J., (1995) Inorg. Chem., 34, p. 4326
  • Callahan, R.W., Keene, F.R., Meyer, T.J., Salmon, D.J., (1977) J. Am. Chem. Soc., 99, p. 1064
  • Coe, B.J., Meyer, T.J., White, P.S., (1995) Inorg. Chem., 34, p. 593
  • Neyhart, G.A., Hupp, J.T., Curtis, J.C., Timpson, C.J., Meyer, T.J., (1996) J. Am. Chem. Soc., 118, p. 3724
  • Neyhart, G.A., Timpson, C.J., Bates, W.D., Meyer, T.J., (1996) J. Am. Chem. Soc., 118, p. 3730
  • Hupp, J.T., Kober, E.M., Neyhart, G.A., Meyer, T.J., (1991) Mixed Valency Systems-Applications in Chemistry, Physics and Biology, p. 51. , Prassides, K., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands
  • Stebler, A., Ammeter, J.H., Fürholz, U., Ludi, A., (1984) Inorg. Chem., 23, p. 2764
  • Citrin, P.H., (1973) J. Am. Chem. Soc., 95, p. 6472
  • Citrin, P.H., Ginsberg, A.P., (1981) J. Am. Chem. Soc., 103, p. 3673
  • Oh, D.H., Boxer, S.G., (1990) J. Am. Chem. Soc., 112, p. 8161
  • Best, S.P., Clark, R.J.H., McQueen, R.C.S., Joss, S., (1989) J. Am. Chem. Soc., 111, p. 548
  • Zhang, L.-T., Ko, J., Ondrechen, M.J., (1987) J. Am. Chem. Soc., 109, p. 1666
  • Ondrechen, M.J., Ko, J., Zhang, L.-T., (1987) J. Am. Chem. Soc., 109, p. 1672
  • Bersuker, I.B., (1996) Electronic Structure and Properties of Transition Metal Compounds, p. 531. , Wiley: New York
  • Schatz, P.N., (1991) Mixed Valency Systems-Applications in Chemistry, Physics and Biology, p. 7. , Prassides, K., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands
  • Reimers, J.R., Hush, N.S., (1991) Mixed Valency Systems-Applications in Chemistry, Physics and Biology, p. 29. , Prassides, K., Ed.; Kluwer Academic Publishers: Dordrecht, the Netherlands
  • Piepho, S.B., (1991) Mixed Valency Systems-Applications in Chemistry, Physics and Biology, p. 329. , Prassides, K., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands
  • Borshch, S.A., Kotov, I.N., (1991) Mixed Valency Systems-Applications in Chemistry, Physics and Biology, p. 347. , Prassides, K., Ed.; Kluwer: Dordrecht, The Netherlands
  • Slep, L.D., Baraldo, L.M., Olabe, J.A., (1996) Inorg. Chem, 35, p. 6327
  • Waldhör, E., Kaim, W., Olabe, J.A., Slep, L.D., Fiedler, J., (1997) Inorg. Chem., 36, p. 2969
  • Connelly, N.G., Geiger, W.E., (1996) Chem. Rev., 96, p. 877
  • Krejcik, M., Danek, M., Hartl, F., (1991) J. Eleclroanal. Chem. Interfacial Electrochem., 317, p. 179
  • Kaim, W., Ernst, S., Kasack, V., (1990) J. Am. Chem. Soc., 112, p. 173
  • Reichardt, 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
  • Creutz, C., Chou, M.H., (1987) Inorg. Chem., 26, p. 2995
  • Kaim, W., Reinhardt, R., Sieger, M., (1994) Inorg Chem., 33, p. 4453
  • Kaim, W., (1983) Angew. Chem., 95, p. 201
  • (1983) Angew. Chem., Int. Ed. Engl., 22, p. 171
  • Olbrich-Deussner, B., Gross, R., Kaim, W., (1989) J. Organomet. Chem., 366, p. 155
  • Olbrich-Deussner, B., Kaim, W., Gross-Lannert, R., (1989) Inorg. Chem., 28, p. 3113
  • Atwood, C.G., Geiger, W.E., (1993) J. Am. Chem. Soc., 115, p. 5310
  • Van Order Jr., N., Bitterwolf, T.E., Rheingold, A.L., Geiger, W.E., (1987) J. Am. Chem. Soc., 109, p. 5680
  • Geiger, W.E., Van Order Jr., N., Pierce, D.T., Bitterwolf, T.E., Rheingold, A.L., Chasteen, N.D., (1991) Organometallics, 10, p. 2403
  • Geiger, W.E., Atwood, C.G., Chin, T.T., (1993) Molecular Electrochemistry of Inorganic, Bioinorganic and Organometollic Compounds, p. 519. , Pombeiro, A. J. L., McCleverty, J. A., Eds.; Kluwer Academic Publishers: Dordrecht, The Netherlands
  • Merkert, J.W., Geiger, W.E., Paddon-Row, M.N., Oliver, A.M., Rheingold, A.L., (1992) Organometallics, 11, p. 4109
  • Pierce, D.T., Geiger, W.E., (1994) Inorg. Chem., 33, p. 373
  • Kang, H.W., Moran, G., Krausz, E., (1996) Inorg. Chim. Acta, 249, p. 231
  • Kaim, W., (1987) Coord. Chem. Rev., 76, p. 187
  • Kober, E.M., Meyer, T.J., (1982) Inorg. Chem., 27, p. 3966
  • Goodman, B.A., Raynor, J.B., (1970) Adv. Inorg. Chem. Radiochem, 13, p. 135
  • Kasack, V., Kaim, W., Jordanov, J., Roth, E.K.H., Manuscript in preparation; Heilmann, M., (1997), Ph.D. Thesis, Universität Stuttgart; Curtis, J.C., Sullivan, B.P., Meyer, T.J., (1983) Inorg. Chem., 23, p. 224. , Solvent effects for cationic mixed-valent systems

Citas:

---------- APA ----------
Hornung, F.M., Baumann, F., Kaim, W., Olabe, J.A., Slep, L.D. & Fiedler, J. (1998) . Spectroelectrochemical Characterization of the Two-Step Redox System {(μ-pz)[Os(CN)5]2}n- (n = 4, 5, 6; pz = Pyrazine). Similarities and Differences in Relation to the Creutz-Taube System. Inorganic Chemistry, 37(2), 311-316.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v37_n2_p311_Hornung [ ]
---------- CHICAGO ----------
Hornung, F.M., Baumann, F., Kaim, W., Olabe, J.A., Slep, L.D., Fiedler, J. "Spectroelectrochemical Characterization of the Two-Step Redox System {(μ-pz)[Os(CN)5]2}n- (n = 4, 5, 6; pz = Pyrazine). Similarities and Differences in Relation to the Creutz-Taube System" . Inorganic Chemistry 37, no. 2 (1998) : 311-316.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v37_n2_p311_Hornung [ ]
---------- MLA ----------
Hornung, F.M., Baumann, F., Kaim, W., Olabe, J.A., Slep, L.D., Fiedler, J. "Spectroelectrochemical Characterization of the Two-Step Redox System {(μ-pz)[Os(CN)5]2}n- (n = 4, 5, 6; pz = Pyrazine). Similarities and Differences in Relation to the Creutz-Taube System" . Inorganic Chemistry, vol. 37, no. 2, 1998, pp. 311-316.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v37_n2_p311_Hornung [ ]
---------- VANCOUVER ----------
Hornung, F.M., Baumann, F., Kaim, W., Olabe, J.A., Slep, L.D., Fiedler, J. Spectroelectrochemical Characterization of the Two-Step Redox System {(μ-pz)[Os(CN)5]2}n- (n = 4, 5, 6; pz = Pyrazine). Similarities and Differences in Relation to the Creutz-Taube System. Inorg. Chem. 1998;37(2):311-316.
Available from: https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v37_n2_p311_Hornung [ ]