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Complejos de Ni (I) -Alquilo que contienen ligandos de fenantrolina: evidencia experimental para la inserción de CO2

Rosie J Somerville^1,2, Carlota Odena^1,2, Marc F Obst³

¹Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain.

Journal of the American Chemical Society

|June 11, 2020

Resumen

Los investigadores sintetizaron complejos esquivos de níquel-alquilo, intermedios cruciales en las reacciones catalizadas por níquel. Este trabajo aclara su reactividad con el dióxido de carbono, respondiendo preguntas clave en la carboxilación catalítica.

Área de la Ciencia:

Química organometálica
Catálisis
Química sintética

Sus antecedentes:

Las reacciones de acoplamiento cruzado catalizadas por níquel son vitales en la síntesis orgánica.
El papel de los intermediarios de níquel (I) -alquilo en estas reacciones sigue siendo especulativo.
La comprensión de estos intermedios es clave para avanzar en la carboxilación catalítica.

Objetivo del estudio:

Síntesis y caracterización de las especies difíciles de alcanzar (fenantrolina) Ni (I) -alquilo.
Investigar la reactividad de estas especies de Ni (I) con el dióxido de carbono (CO2).
Para resolver preguntas de larga data con respecto a los mecanismos de carboxilación catalizados por Ni.

Principales métodos:

Síntesis de complejos específicos de (fenantrolina) Ni (I) alquilo.
Caracterización espectroscópica de las especies sintetizadas.
Estudios de reactividad que implican la adición de CO2 a los complejos de Ni.

Principales resultados:

Síntesis y aislamiento exitosos de los intermediarios (fenantrolina) Ni (I) -alquilo propuestos.
Demostración de la reactividad de estas especies de Ni (I) con el CO2.
Evidencia directa que apoya la participación de las especies de Ni (I) -alquilo en la carboxilación.

Conclusiones:

Se han sintetizado las especies difíciles de alcanzar (fenantrolina) Ni (I) -alquilo.
Estos intermedios reaccionan con el CO2, confirmando su papel propuesto en la carboxilación catalizada por Ni.
Este estudio proporciona información crítica sobre el mecanismo de las reacciones de carboxilación catalizadas por níquel.

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