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[tBu2PCH2SiMe2) 2N]RuCH3: el origen de una activación extremadamente fácil, doble H-C (sp3) que genera un complejo

Michael J Ingleson¹, Xiaofan Yang, Maren Pink

¹Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, IN, USA.

Journal of the American Chemical Society

|August 4, 2005

Resumen

Un nuevo complejo de rutenio activa rápidamente enlaces C-H a bajas temperaturas, formando un intermediario hidrido-carbeno. Este descubrimiento arroja luz sobre las vías de eliminación del metano y la reactividad organometálica.

Área de la Ciencia:

Química organometálica Química orgánica de los metales.
La catálisis por catálisis.
Química computacional es la química computacional.

Sus antecedentes:

Los complejos de rutenio son vitales en la catálisis.
Comprender la activación de C-H es clave para desarrollar nuevos métodos sintéticos.
Los complejos metálicos de baja coordinación ofrecen una reactividad única.

Objetivo del estudio:

Para investigar la reactividad de un complejo de rutenio de cuatro coordenadas.
Para aclarar el mecanismo de la activación de C-H y la eliminación de metano.
Para caracterizar el intermediario hidrido-carbeno resultante.

Principales métodos:

Síntesis y caracterización del complejo [tBu2PCH2SiMe2)2N]RuCH3.
Experimentos de activación de H-C ((sp3) a baja temperatura.
Cálculos de la Teoría Funcional de la Densidad (DFT).

Principales resultados:

El complejo de rutenio se somete a una rápida activación doble H-C(sp3) a -78 °C.
Se generó un nuevo complejo "hidrido-carbeno".
Los cálculos de DFT revelaron una baja barrera de activación debido a una interacción alfa-agóstica.

Conclusiones:

El complejo hidrido-carbeno es un estado de reposo "enmascarado" de un complejo alquilo ciclometalizado.
La migración de hidruro precede a la reactividad posterior en este sistema.
Los hallazgos proporcionan información sobre los mecanismos de eliminación de metano de baja barrera.

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