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Un complejo dicoordinado de paladio (((0) con una inusual coordinación intramolecular eta (((1) -areno

Steven M Reid¹, Robert C Boyle, Joel T Mague

¹Department of Chemistry, Tulane University, New Orleans, Louisiana 70118, USA.

Journal of the American Chemical Society

|June 26, 2003

Resumen

Se sintetizó y caracterizó un nuevo complejo de paladio, bis ((dicyanobiphenyl) paladio ((0) o (dcpBiph) 2Pd). Este complejo de paladio de baja coordinación exhibe características estructurales únicas y reactividad en reacciones de activación de enlaces C-X.

Área de la Ciencia:

Química organometálica de las sustancias orgánicas.
La química de la coordinación es química de la coordinación.
La catálisis es la catálisis.

Sus antecedentes:

Los complejos de paladio son cruciales en la catálisis.
Las especies de paladio de baja coordinación ofrecen una reactividad única.
Los ligandos de fosfina bidentada pueden estabilizar geometrías de coordinación inusuales.

Objetivo del estudio:

Para sintetizar y caracterizar un nuevo complejo de paladio de baja coordenada.
Investigar las características estructurales del complejo sintetizado en estado sólido y en solución.
Para explorar la reactividad del complejo en reacciones de adición oxidativa.

Principales métodos:

Síntesis de bis ((dicianobifenil) paladio ((0) de (tmeda) PdMe2 y dcpBiph.ph desde (tmeda) PdMe2 y dcpBiph.
Cristalografía de rayos X para la determinación de la estructura en estado sólido.
Espectroscopia de RMN de solución para identificar diferentes conformadores.
Estudios de reacción con varios haluros de arilo (PhX).

Principales resultados:

Se logró la síntesis de alto rendimiento de (dcpBiph) 2Pd.
La estructura de estado sólido reveló un ángulo p-pd-p doblado y una interacción eta1-areno.
Los estudios de solución indicaron la presencia de un conformador adicional sin interacción pi-areno.
(dcpBiph) 2Pd se sometió a una adición oxidativa con PhI, PhBr y PhCl.
Se observó un producto menor de la metalización del anillo de bifenilo.

Conclusiones:

El complejo sintetizado (dcpBiph) 2Pd es una especie estable de paladio de baja coordinación.
El complejo exhibe dinámicas estructurales interesantes en estado sólido versus solución.
El complejo demuestra reactividad hacia la activación de enlaces C-X, relevante para aplicaciones catalíticas.

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