Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers

We report here the synthesis and properties of a family of mixed-valence cyanide-bridged dinuclear complex ions trans-[(L′L4Ru II(μ-NC)FeIII(CN)5]- (with L = pyridine or 4-dimethylaminopyridine (dmap) and L′ = pyridine, 4-methoxypyridine (meopy) or 4-dimethylaminopyridine)) whose properties could be...

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Autor principal: Rossi, M.B
Otros Autores: Alborés, P., Baraldo, L.M
Formato: Capítulo de libro
Lenguaje:Inglés
Publicado: 2011
Acceso en línea:Registro en Scopus
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100 1 |a Rossi, M.B. 
245 1 0 |a Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers 
260 |c 2011 
270 1 0 |m Baraldo, L.M.; Departamento de Química Analítica, Inorgánica y Química Física, Facultad de Ciencias Exactas y Naturales, Pabellón 2, C1428EHA Buenos Aires, Argentina; email: baraldo@qi.fcen.uba.ar 
506 |2 openaire  |e Política editorial 
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520 3 |a We report here the synthesis and properties of a family of mixed-valence cyanide-bridged dinuclear complex ions trans-[(L′L4Ru II(μ-NC)FeIII(CN)5]- (with L = pyridine or 4-dimethylaminopyridine (dmap) and L′ = pyridine, 4-methoxypyridine (meopy) or 4-dimethylaminopyridine)) whose properties could be adjusted smoothly by changing the acceptor properties of the solvent and the σ donor properties of the L′ pyridine ligand. In solution these complexes exhibit an intense solvent-dependent MM′CT (RuII → FeIII) absorption in the near infrared region. Analysis of this band in different complexes and solvents suggests an enhanced interaction as the energies of the metal centers come closer. From this trend the anion trans-[(dmap)5Ru(μ-NC)Fe(CN)5]- (dmap = 4-dimethylaminopyridine) in water is expected to belong to the class II-III, but its spectral properties indicates a ground state with Ru(III)-Fe(II) character. The stabilization of this electronic isomer is probably related to the better donor properties of the hexacyanoferrate(II) moiety and its stronger interaction with water. © 2011 Elsevier B.V. All rights reserved.  |l eng 
536 |a Detalles de la financiación: Universidad de Buenos Aires 
536 |a Detalles de la financiación: Consejo Nacional de Investigaciones Científicas y Técnicas 
536 |a Detalles de la financiación: The authors thank the University of Buenos Aires and the Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET) for economic funding. P. A. and L. B. V are members of the scientific staff of CONICET. M.B.R. is a graduate fellow of CONICET. Appendix A 
593 |a Departamento de Química Analítica, Inorgánica y Química Física, Facultad de Ciencias Exactas y Naturales, Pabellón 2, C1428EHA Buenos Aires, Argentina 
690 1 0 |a CYANIDE BRIDGED COMPLEXES 
690 1 0 |a INTERVALENCE CHARGE TRANSFER 
690 1 0 |a METAL-METAL INTERACTION 
690 1 0 |a MIXED VALENCE COMPLEXES 
690 1 0 |a SOLVENT EFFECT 
690 1 0 |a SPECTROELECTROCHEMISTRY 
700 1 |a Alborés, P. 
700 1 |a Baraldo, L.M. 
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