Class III Delocalization in a Cyanide-Bridged Trimetallic Mixed-Valence Complex

The NIR and IR spectroscopic properties of the cyanide-bridged complex, trans-[Ru(dmap)4{(μ-CN)Ru(py)4Cl}2]3+ (py=pyridine, dmap=4-dimethylaminopyridine) provide strong evidence that this trimetallic ion behaves as a Class III mixed-valence species, the first example reported of a cyanide-bridged sy...

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Detalhes bibliográficos
Autores: Pieslinger, German Eduardo, Alborés, Pablo, Slep, Leonardo Daniel, Baraldo Victorica, Luis Mario
Tipo de documento: artigo
Estado:Versão publicada
Data de publicação:2013
País:Argentina
Recursos:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositório:CONICET Digital (CONICET)
Idioma:inglês
OAI Identifier:oai:ri.conicet.gov.ar:11336/30704
Acesso em linha:http://hdl.handle.net/11336/30704
Access Level:Acceso aberto
Palavra-chave:Cyanometalates
Density Functional Calculations
Metal-Metal Interaction
Mixed-Valence Compounds
Ruthenium
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
Descrição
Resumo:The NIR and IR spectroscopic properties of the cyanide-bridged complex, trans-[Ru(dmap)4{(μ-CN)Ru(py)4Cl}2]3+ (py=pyridine, dmap=4-dimethylaminopyridine) provide strong evidence that this trimetallic ion behaves as a Class III mixed-valence species, the first example reported of a cyanide-bridged system. This has been accomplished by tuning the energy of the fragments in the trimetallic complex to compensate for the intrinsic asymmetry of the cyanide bridge. Moreover, (TD)DFT calculations accurately predict the spectra of the trans-[Ru(dmap)4{(μ-CN)Ru(py)4Cl}2]3+ ion and confirms its delocalized nature.