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Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
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Complejación y liberación de ligandos N-heterocíclicos de carbeno-aminoborileno de los metales de los grupos VI y
Conor Pranckevicius1,2, J Oscar C Jimenéz-Halla3, Marius Kirsch1,2
1Institute for Inorganic Chemistry , Julius-Maximilians-Universität Würzburg, Am Hubland , 97074 Würzburg , Germany.
Journal of the American Chemical Society
|July 27, 2018
Resumen
Los nuevos ligandos de aminoborileno, estabilizados por carbenos N-heterocíclicos (NHC), forman complejos metálicos robustos. Estos ligandos son altamente liberadores de electrones y nucleófilos, ofreciendo estabilidad y reactividad únicas en la química de coordinación.
Área de la Ciencia:
- Química organometálica
- Química del grupo principal
- Diseño del ligando
Sus antecedentes:
- Los carbenos N-heterocíclicos (NHC) son ligandos versátiles en la química de la coordinación.
- Los aminoborilenos son una clase de ligandos que contienen boro con propiedades electrónicas únicas.
- La comprensión de la estabilidad y la reactividad de los complejos metal-borileno es crucial para el desarrollo de nuevos sistemas catalíticos.
Objetivo del estudio:
- Investigar la química de coordinación y la estabilidad de los ligandos de aminoborileno con diferentes grupos estabilizadores de carbenos N-heterocíclicos (NHC).
- Síntesis y caracterización de nuevos complejos metal-aminoborileno.
- Comparar las propiedades electrónicas y la reactividad de los aminoborilenos estabilizados por NHC con otros ligandos.
Principales métodos:
- Síntesis de complejos de NHC-aminoborileno mediante la reducción de los aductos de NHC-dihaloaminoborane.
- Utilización de las especies de hexacarbonilo de sodio M (M = Fe, Ru, Cr, W) como agentes reductores.
- Caracterización mediante espectroscopia infrarroja y cristalografía de rayos X (implicada).
Principales resultados:
- Los ligandos de aminoborileno estabilizados con imidazol-2-ilideno formaron complejos de metal-borileno térmicamente robustos e inertes.
- Se encontró que estos ligandos son más liberadores de electrones y nucleófilos que los NHC clásicos.
- Los dihaloaminoboranes ligados al alquilaminocarbeno cíclico (CAAC) produjeron radicales centrados en el boro o aminoborilenos estabilizados con carbonio.
- Se observó la migración de borileno a CO en un complejo de rutenio.
Conclusiones:
- Los aminoborilenos estabilizados por NHC son ligandos efectivos para crear complejos metálicos estables y únicos.
- Las propiedades electrónicas del grupo estabilizador NHC influyen significativamente en la reactividad y estabilidad de los complejos metal-borileno resultantes.
- Los aminoborilenos representan una nueva clase de ligandos con aplicaciones potenciales en la catálisis y la ciencia de los materiales.
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