Electrochemical triggered O-atom transfer reaction in nitrocarbonyl rhenium(I) complexes: An IR spectroelectrochemical investigation

In previous work we proposed that polypyridylrhenium(I)tricarbonyl complexes coordinated to ion nitrite through its N-atom in CH2Cl2 solution could give nitrosyl complexes by electrochemical oxidation. In this work, we report for the first time by IR-spectroelectrochemical measurements that when [Re...

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Detalles Bibliográficos
Autores: Domínguez, Sofía Eugenia, Fagalde, Florencia
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2015
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/6737
Acceso en línea:http://hdl.handle.net/11336/6737
Access Level:acceso abierto
Palabra clave:Polypyridyl Rhenium(I)Tricarbonyl
Nitrosyl Complexes
Ir Spectroelectrochemistry
O-Atom Transfer Reaction
Electrochemical Oxidation
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
Descripción
Sumario:In previous work we proposed that polypyridylrhenium(I)tricarbonyl complexes coordinated to ion nitrite through its N-atom in CH2Cl2 solution could give nitrosyl complexes by electrochemical oxidation. In this work, we report for the first time by IR-spectroelectrochemical measurements that when [ReI(L)(CO)3(NO2)] oxidized to [ReI(L)(CO)3(NO2)]+ with L=2,2′-bipyridine (bpy) and 4,4′-dimethyl-2,2′-bipyridine (dmb), an O-atom transfer reaction occurs triggered by electrochemical oxidation, leading to a complex with a Re(CO)2(NO) structure and releasing CO2 by an intramolecular mechanism. Additionally, the Re-based oxidation and bipyridyl-based reduction of the nitro-complexes were investigated. The experimental results are in agreement with computational analysis calculated by DFT methods.