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Un complejo enmascarado de cobalto de dos coordenadas que activa los enlaces C-F

Thomas R Dugan¹, Xianru Sun, Elena V Rybak-Akimova

¹Department of Chemistry, University of Rochester, Rochester, New York 14627, United States.

Journal of the American Chemical Society

|July 21, 2011

Resumen

Los investigadores aislaron y caracterizaron un nuevo complejo de cobalto, LtBuCo, que presenta un ligando único que le permite actuar como una especie enmascarada de dos coordenadas. Este complejo es un sintón estable para el cobalto de baja coordinación (I) y puede cortar enlaces carbono-fluoro.

Área de la Ciencia:

Química organometálica Química orgánica de los metales.
Coordinación Química de la Coordinación
Diseño del ligando diseño de ligando.

Sus antecedentes:

Los complejos metálicos de baja coordinación son cruciales para las aplicaciones catalíticas.
Los ligandos voluminosos a menudo se emplean para estabilizar los centros metálicos reactivos.
La comprensión de los modos de unión de ligandos es clave para controlar la reactividad.

Objetivo del estudio:

Para aislar y caracterizar un nuevo complejo de cobalto insaturado con un voluminoso ligando beta-diketiminado.
Para investigar el inusual modo de unión del areno deslizado y su interconversión con la ligadura tradicional.
Demostrar la utilidad de este complejo como sintón para cobalto de baja coordenada (I) y su reactividad hacia la escisión de enlaces C-F.

Principales métodos:

El aislamiento y la caracterización completa del complejo LtBuCo.
Estudios cinéticos para dilucidar el mecanismo de isomerización del ligando.
Estudios de reactividad, incluida la activación del enlace C-F del fluorobenzeno.

Principales resultados:

Aislamiento y caracterización exitosos de L(tBu) Co.
Descubrimiento de una rápida interconversión entre el deslizamiento de κN,η(6)-areno y los tradicionales modos de unión κ(2) N,N'.
Demostración de L{tBu) Co como un sintón estable pero reactivo para cobalto de baja coordinación{I).
Evidencia de la escisión del enlace C-F en el fluorobenzeno por el complejo.

Conclusiones:

El voluminoso ligando beta-diketiminato permite una especie "enmascarada" de cobalto de dos coordenadas.
La isomerización de ligandos es reversible y está controlada por la coordinación de bases de Lewis.
L ((tBu) Co representa una nueva herramienta valiosa para explorar la química del cobalto de baja coordinación y la activación del enlace C-F.

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