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Inserción de imina en un enlace metal-carbono tardío para formar un complejo de amido estable
Christopher Krug1, John F Hartwig
1Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.
Journal of the American Chemical Society
|March 5, 2004
Resumen
Un nuevo complejo de aril rodio (I) reacciona con las aril iminas, formando productos estables de inserción de amida de rodio. Otras reacciones revelan vías complejas que implican la eliminación de beta-hidrógeno y la ciclometalización, produciendo aminas y ketiminas.
Área de la Ciencia:
- Química organometálica Química orgánica de los metales.
- La catálisis de la catálisis.
- Química sintética de la química sintética.
Sus antecedentes:
- Los complejos de arilrodio (I) son catalizadores versátiles.
- Comprender la reactividad de los ligandos es crucial para desarrollar nuevos métodos sintéticos.
Objetivo del estudio:
- Para sintetizar y caracterizar un nuevo arylrhodium (I) complejo.
- Para investigar la reactividad de este complejo con varias aril-iminas.
- Para dilucidar los mecanismos de reacción e identificar los intermediarios clave.
Principales métodos:
- Síntesis de un complejo de arilrodio (I) utilizando reactivos de organolitio y un precursor de rodio.
- Reacción del complejo de rodio con diferentes iminas de arilo.
- Caracterización de productos utilizando difracción de rayos X de un solo cristal.
- Estudios mecanicistas que incluyen análisis de producto y aislamiento intermedio.
Principales resultados:
- Aislamiento de un complejo estable de arilirodio (I), (DPPE) Rh (C5H5N) y p-tol.
- Observación de la inserción de imina en el enlace Rh-arilo, formando productos de amida Rh.
- Identificación de una vía de reacción que implica la eliminación de beta-hidrógeno y la ciclometalización para iminas neutras en electrones y ricas en electrones.
- Aislamiento y caracterización de un intermediario del ciclo metálico.
Conclusiones:
- El complejo arilrodio (I) exhibe una reactividad diversa con las iminas de arilo.
- Un mecanismo de varios pasos que involucra la inserción, eliminación y ciclometalización gobierna la formación del producto.
- La caracterización estructural proporciona información sobre los intermediarios y vías de reacción.
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