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Un complejo bimetálico Ru2Pt que contiene un ligando mu3-carbido trigonal-planar: formación, estructura y reactividad
Shin Takemoto1, Hidenobu Morita, Kenji Karitani
1Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Gakuen-cho 1-1, Naka-ku, Sakai, Osaka 599-8531, Japan. takemoto@c.s.osakafu-u.ac.jp
Journal of the American Chemical Society
|December 17, 2009
Resumen
Se sintetizó un nuevo complejo bimetálico rutenio-platino con un ligando de carbido plano. Este complejo de carbido reacciona con el monóxido de carbono para formar nuevos complejos de dirutenio y platino.
Área de la Ciencia:
- Química organometálica Química orgánica de los metales.
- Coordinación Química de la Coordinación
- La catálisis es la catálisis.
Sus antecedentes:
- Los complejos bimetálicos ofrecen una reactividad única debido a los efectos cooperativos entre los centros metálicos.
- Los ligandos carbido son especies raras y altamente reactivas en la química organometálica.
- Comprender la síntesis y la reactividad de los complejos de carbido es crucial para desarrollar nuevas transformaciones catalíticas.
Objetivo del estudio:
- Para sintetizar y caracterizar un nuevo complejo bimetálico rutenio-platino con un ligando carbido planar de tres coordenadas.
- Para investigar la reactividad del ligando de carbido hacia moléculas pequeñas como el monóxido de carbono.
- Para dilucidar las características estructurales de los complejos sintetizados a través de la cristalografía de rayos X.
Principales métodos:
- Isomerización térmica de un precursor de metileno puente para formar el complejo carbido.
- Reacción del complejo carbido con el monóxido de carbono.
- Aislamiento y caracterización de productos utilizando técnicas como la cristalografía de rayos X.
- Determinación del rendimiento para la síntesis del complejo carbido.
Principales resultados:
- El complejo bimetálico de carbido de rutenio-platino [Cp*Ru) 2 Mu 2 NHPh) 3 Mu 2 H) 3 Mu 3 C) PtMe 3 PMe 3] 2 [OTf] 3 fue sintetizado con un rendimiento del 93%.
- La exposición del complejo de carbido 3 al monóxido de carbono condujo a la formación de un complejo de dirutenio etilideno [(Cp*Ru) (((2) (((mu(2) -CHMe) (((mu(2) -NHPh) ((CO) (((2) [OTf] (4) y un complejo de triplatino.
- Se determinaron las estructuras cristalinas del precursor, el complejo de carbido y el complejo de etilideno.
Conclusiones:
- La isomerización térmica proporciona una ruta eficiente a los ligandos planos de carbido en sistemas bimetálicos.
- El ligando carbido es reactivo hacia el monóxido de carbono, lo que lleva al acoplamiento de ligandos y la formación de nuevas especies organometálicas.
- Los complejos reportados muestran interesantes motivos estructurales y patrones de reactividad relevantes para la síntesis y catálisis organometálicas.
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