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

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 reversib...

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Autores principales: Scheiring, T., Kaim, W., Olabe, J.A., Parise, A.R., Fiedler, J.
Formato: JOUR
Materias:
Cyano complexes
Mixed-valence complexes
Ruthenium complexes
Spectroelectrochemistry
pyrazine derivative
ruthenium derivative
article
complex formation
Czech Republic
electrochemistry
Germany
molecular interaction
oxidation reduction reaction
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_00201693_v300-302_n_p125_Scheiring
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling todo:paper_00201693_v300-302_n_p125_Scheiring2023-10-03T14:17:16Z 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 Scheiring, T. Kaim, W. Olabe, J.A. Parise, A.R. Fiedler, J. Cyano complexes Mixed-valence complexes Ruthenium complexes Spectroelectrochemistry pyrazine derivative ruthenium derivative article complex formation Czech Republic electrochemistry Germany molecular interaction oxidation reduction reaction 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. Fil:Olabe, J.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Parise, A.R. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00201693_v300-302_n_p125_Scheiring
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Cyano complexes
Mixed-valence complexes
Ruthenium complexes
Spectroelectrochemistry
pyrazine derivative
ruthenium derivative
article
complex formation
Czech Republic
electrochemistry
Germany
molecular interaction
oxidation reduction reaction
spellingShingle Cyano complexes
Mixed-valence complexes
Ruthenium complexes
Spectroelectrochemistry
pyrazine derivative
ruthenium derivative
article
complex formation
Czech Republic
electrochemistry
Germany
molecular interaction
oxidation reduction reaction
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
topic_facet Cyano complexes
Mixed-valence complexes
Ruthenium complexes
Spectroelectrochemistry
pyrazine derivative
ruthenium derivative
article
complex formation
Czech Republic
electrochemistry
Germany
molecular interaction
oxidation reduction reaction
description 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.
format JOUR
author Scheiring, T.
Kaim, W.
Olabe, J.A.
Parise, A.R.
Fiedler, J.
author_facet Scheiring, T.
Kaim, W.
Olabe, J.A.
Parise, A.R.
Fiedler, J.
author_sort Scheiring, T.
title 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
title_short 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
title_full 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
title_fullStr 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
title_full_unstemmed 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
title_sort 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
url http://hdl.handle.net/20.500.12110/paper_00201693_v300-302_n_p125_Scheiring
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