C-NH2 bond formation mediated by iridium complexes
In the presence of phosphanes (PR3), the amido-bridged trinuclear complex [{Ir(μ-NH2)(tfbb)}3] (tfbb=tetrafluorobenzobarrelene) transforms into mononuclear discrete compounds [Ir(1,2-η2-4-κ-C12H8F 4N)(PR3)3], which are the products of the C-N coupling between the amido moiety and a vinylic carbon of...
| Autores: | , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2014 |
| País: | España |
| Institución: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/111842 |
| Acceso en línea: | http://hdl.handle.net/10261/111842 |
| Access Level: | acceso abierto |
| Palabra clave: | C-N formation Amido transfer N-H activation Iridium Ammonia |
| Sumario: | In the presence of phosphanes (PR3), the amido-bridged trinuclear complex [{Ir(μ-NH2)(tfbb)}3] (tfbb=tetrafluorobenzobarrelene) transforms into mononuclear discrete compounds [Ir(1,2-η2-4-κ-C12H8F 4N)(PR3)3], which are the products of the C-N coupling between the amido moiety and a vinylic carbon of the diolefin. An alternative synthetic approach to these species involves the reaction of the 18-e- complex [Ir(Cl)(tfbb)(PMePh2)2] with gaseous ammonia and additional phosphane. DFT studies show that both transformations occur through nucleophilic attack. In the first case the amido moiety attacks a diolefin coordinated to a neighboring molecule following a bimolecular mechanism induced by the highly basic NH2 moiety; the second pathway involves a direct nucleophilic attack of ammonia to a coordinated tfbb molecule. |
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