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Ligandos fuertemente coordinados para formar aniones organometálicos débilmente coordinados pero funcionales
Steven P Fisher1, Scott G McArthur1, Varun Tej1
1Department of Chemistry and Center for Catalysis , University of California-Riverside , Riverside , California 92521 , United States.
Journal of the American Chemical Society
|December 6, 2019
Resumen
Los aniones organometálicos funcionales actúan como aniones de coordinación débil y catalizadores. Los nuevos carboraniles polihalogenados NHC mejoran la estabilidad y la actividad catalítica en las reacciones de hidroaminación.
Área de la Ciencia:
- Química organometálica
- Catálisis
- Diseño de aniones
Sus antecedentes:
- Los aniones de coordinación débil (WCAs) tradicionalmente carecen de funciones funcionales.
- Los carbenos N-heterocíclicos (NHC) son ligandos versátiles en la química organometálica.
Objetivo del estudio:
- Desarrollar NHC dianiónicos fuertemente coordinados como ACC funcionales.
- Para crear nuevos complejos organometálicos de Au (I) con doble WCA y propiedades catalíticas.
Principales métodos:
- Síntesis de carboranilos dianiónicos y sus complejos Au ((I).
- Desarrollo de carboraniles polihalogenados para una mayor estabilidad.
- Investigación de la actividad catalítica en la hidroaminación de las alquinas.
Principales resultados:
- Formación de pares de iones heterometálicos y organometálicos/del grupo principal mediante WCAs organometálicos.
- Demostración de la estabilidad superior de los carboranilos polihalogenados.
- Se obtiene una alta actividad catalítica en la hidroaminación de alquinos.
- Se informó el primer centro de baja coordenada Au (III) y el primer verdadero carbeno dianiónico.
Conclusiones:
- Los WCAs organometálicos pueden poseer funciones tanto de espectador como de catalizador.
- Los NHC de carboranilo polihalogenado ofrecen mayor estabilidad y rendimiento catalítico.
- Estos hallazgos permiten el diseño de pares de iones funcionales para la catálisis cooperativa.
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