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

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...

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Autor principal: Hornung, F.M
Otros Autores: Baumann, F., Kaim, W., Olabe, J.A, Slep, L.D, Fiedler, J.
Formato: Capítulo de libro
Lenguaje:Inglés
Publicado: 1998
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030 |a INOCA 
100 1 |a Hornung, F.M. 
245 1 0 |a 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 
260 |c 1998 
270 1 0 |m Kaim, W.; Inst. für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany 
506 |2 openaire  |e Política editorial 
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520 3 |a 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.  |l eng 
593 |a Inst. für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70550 Stuttgart, Germany 
593 |a Depto. de Quim. Inorgánica, Fac. de Cie. Exactas/Naturales, UBA, Pabellón 2, Cd. Universitaria, Buenos Aires, Capital Federal 1428, Argentina 
593 |a J. Heyrovsky Inst. of Phys. Chem., Acad. of Sciences of Czech Republic, Dolejškova 3, CZ-18223 Prague, Czech Republic 
700 1 |a Baumann, F. 
700 1 |a Kaim, W. 
700 1 |a Olabe, J.A. 
700 1 |a Slep, L.D. 
700 1 |a Fiedler, J. 
773 0 |d 1998  |g v. 37  |h pp. 311-316  |k n. 2  |p Inorg. Chem.  |x 00201669  |w (AR-BaUEN)CENRE-60  |t Inorganic Chemistry 
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