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Estudio de síntesis y eliminación reductora de N-H de complejos de dihidruro de imido de rutenio dinuclear complejos

Shin Takemoto¹, Yusuke Yamazaki, Takahiro Yamano

¹Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Gakuen-cho 1-1, Naka-ku, Sakai, Osaka 599-8531, Japan.

Journal of the American Chemical Society

|September 15, 2012

Resumen

Se sintetizaron nuevos complejos de dihidruro imido de dirutenio. La eliminación reductiva de los enlaces N-H en estos complejos da lugar a complejos de amidohidruro, con conocimientos mecanicistas respaldados por cálculos de DFT y estudios cinéticos.

Área de la Ciencia:

Química organometálica Química orgánica de los metales.
Los complejos de rutenio.
La catálisis de la catálisis.

Sus antecedentes:

Los complejos de dihidruro de imido de dirutenio son importantes intermediarios en varias reacciones catalíticas.
Comprender su reactividad es crucial para desarrollar nuevas metodologías sintéticas.

Objetivo del estudio:

Para sintetizar nuevos complejos de dihidruro de dirutenio imido.
Investigar el mecanismo de eliminación reductora de enlaces N-H de estos complejos.
Explorar el papel del atrapamiento de areno en la estabilización de los intermediarios reactivos.

Principales métodos:

Síntesis de complejos de dihidruro imido de dirutenio a través de la hidrogenación.
Estudio de las reacciones de eliminación reductoras de N-H en presencia de arenos.
Estudios cinéticos y mediciones del efecto del isótopo cinético.
Cálculos de la Teoría Funcional de Densidad (DFT) para elucidación mecanicista.

Principales resultados:

La síntesis exitosa de los complejos de dihidruro de imido de dirutenio [(Cp*Ru)(2)(μ-NAr)(μ-H)(2)].
Observación de la eliminación reductora de N-H que produce complejos de hidróxido de amido con arenas π-unidas.
Identificación de una especie coordinativamente insaturada de amidohidruro {(Cp*Ru)(2)(μ-NHAr)(μ-H)} (A) como un intermediario clave.
La evidencia para A a través de la interconversión reversible con un complejo tetranuclear.
Los cálculos de DFT revelaron dos vías distintas para la eliminación reductiva de N-H.

Conclusiones:

La eliminación reductora de N-H procede a través de una etapa inicial de determinación de la velocidad seguida de una rápida captura de arenas.
El estudio proporciona importantes conocimientos mecanicistas sobre la reactividad de los complejos de imido de dirutenio.
Los cálculos de DFT apoyan las vías de reacción propuestas y la existencia del intermediario clave A.

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