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...
| Autores: | , , |
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| 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 |
| 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. |
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