Properties of the mixed-valence binuclear complex ion, (NH3)5RuIII-NC-OsII(CN)5]-
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 f...
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1994
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paper:paper_00201693_v223_n1-2_p37_Forlano2023-06-08T14:40:47Z Properties of the mixed-valence binuclear complex ion, (NH3)5RuIII-NC-OsII(CN)5]- Forlano, Paula Baraldo Victorica, Luis Mario Olabe Iparraguirre, Jose Antonio Ammine complexes Cyano complexes Mixed-valence complexes Osmium complexes Ruthenium complexes 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. Fil:Forlano, P. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Baraldo, L.M. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Olabe, J.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 1994 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201693_v223_n1-2_p37_Forlano http://hdl.handle.net/20.500.12110/paper_00201693_v223_n1-2_p37_Forlano |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Ammine complexes Cyano complexes Mixed-valence complexes Osmium complexes Ruthenium complexes |
| spellingShingle |
Ammine complexes Cyano complexes Mixed-valence complexes Osmium complexes Ruthenium complexes Forlano, Paula Baraldo Victorica, Luis Mario Olabe Iparraguirre, Jose Antonio Properties of the mixed-valence binuclear complex ion, (NH3)5RuIII-NC-OsII(CN)5]- |
| topic_facet |
Ammine complexes Cyano complexes Mixed-valence complexes Osmium complexes Ruthenium complexes |
| description |
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. |
| author |
Forlano, Paula Baraldo Victorica, Luis Mario Olabe Iparraguirre, Jose Antonio |
| author_facet |
Forlano, Paula Baraldo Victorica, Luis Mario Olabe Iparraguirre, Jose Antonio |
| author_sort |
Forlano, Paula |
| title |
Properties of the mixed-valence binuclear complex ion, (NH3)5RuIII-NC-OsII(CN)5]- |
| title_short |
Properties of the mixed-valence binuclear complex ion, (NH3)5RuIII-NC-OsII(CN)5]- |
| title_full |
Properties of the mixed-valence binuclear complex ion, (NH3)5RuIII-NC-OsII(CN)5]- |
| title_fullStr |
Properties of the mixed-valence binuclear complex ion, (NH3)5RuIII-NC-OsII(CN)5]- |
| title_full_unstemmed |
Properties of the mixed-valence binuclear complex ion, (NH3)5RuIII-NC-OsII(CN)5]- |
| title_sort |
properties of the mixed-valence binuclear complex ion, (nh3)5ruiii-nc-osii(cn)5]- |
| publishDate |
1994 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201693_v223_n1-2_p37_Forlano http://hdl.handle.net/20.500.12110/paper_00201693_v223_n1-2_p37_Forlano |
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AT forlanopaula propertiesofthemixedvalencebinuclearcomplexionnh35ruiiincosiicn5 AT baraldovictoricaluismario propertiesofthemixedvalencebinuclearcomplexionnh35ruiiincosiicn5 AT olabeiparraguirrejoseantonio propertiesofthemixedvalencebinuclearcomplexionnh35ruiiincosiicn5 |
| _version_ |
1768544851602702336 |