Benzonitrile hydrolysis catalyzed by a ruthenium(II) complex

The rate constant for the basic hydrolysis of benzonitrile (PhCN) to benzamide (PhCONH2) in the [RuII(tpy)(bpy)] moiety (tpy = 2,2′:6′,2″-terpyridine, bpy = 2,2′-bipyridine) (kOH = 3.7 × 10-2 M-1s-1) is 5 × 103 times higher than that of the free ligand and two times higher than that corresponding to...

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Detalles Bibliográficos
Autores: Fagalde, Florencia, Lis, Noemi Dora, Katz, Néstor Eduardo
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2002
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/62133
Acceso en línea:http://hdl.handle.net/11336/62133
Access Level:acceso abierto
Palabra clave:Base Hydrolysis
Benzonitrile Complexes
Catalysis
Ruthenium(Ii)
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
Descripción
Sumario:The rate constant for the basic hydrolysis of benzonitrile (PhCN) to benzamide (PhCONH2) in the [RuII(tpy)(bpy)] moiety (tpy = 2,2′:6′,2″-terpyridine, bpy = 2,2′-bipyridine) (kOH = 3.7 × 10-2 M-1s-1) is 5 × 103 times higher than that of the free ligand and two times higher than that corresponding to the analogous acetonitrile complex. This effect is unusual for a transition metal in the (II) oxidation state, and can be attributed to the π-electron acceptor properties of both the polypyridyl ligands and the phenyl group. Since amides, being poor π-acceptor ligands, are rapidly released from the coordination sphere of ruthenium(II), the final product of this process is the [Ru(tpy)(bpy)(OH)]+ complex. The activation parameters for this nitrile hydrolysis have been determined and compare reasonably well with other values for similar reactions.