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La formación mediada por fosfinita-Ni(0) de una especie de fosfuro-Ni(II) -OCOOMe a través de una cooperación poco
Yeong-Eun Kim1, Seohee Oh1, Seji Kim1
1Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701, Republic of Korea.
Journal of the American Chemical Society
|March 24, 2015
Resumen
Los investigadores observaron reacciones reversibles entre las especies de fosfuro-níquel (II) alcóxido y fosfinita-níquel (0). Esto implicó la formación de enlaces P-O y un cambio redox del níquel, revelando una nueva cooperación entre metales y ligandos con ligandos fosfuro.
Área de la Ciencia:
- Química organometálica Química orgánica de los metales.
- Coordinación Química de la Coordinación
- Química Inorgánica La Química Inorgánica es la química inorgánica.
Sus antecedentes:
- Los complejos de níquel con ligandos de fosfina son cruciales en la catálisis.
- Comprender los ligandos redox-activos es clave para desarrollar nuevos ciclos catalíticos.
- Los ligandos fosfuro ofrecen propiedades electrónicas únicas para la coordinación de los metales.
Objetivo del estudio:
- Para investigar las transformaciones reversibles entre el níquel (II) fosfuro y el níquel (II) especies de fosfinita.
- Explorar el papel de la cooperación metal-ligando en las reacciones catalizadas por níquel.
- Para caracterizar los nuevos complejos de níquel formados durante estas transformaciones.
Principales métodos:
- Síntesis de complejos de níquel con ligandos de fosfina.
- Reacciones que involucran anión metoxínico y dióxido de carbono.
- Caracterización espectroscópica de productos intermedios y productos.
- Las titulaciones de redox para determinar la transferencia de electrones.
Principales resultados:
- Formación reversible de enlaces P-O observada entre especies de fosfuro-níquel (II) alcóxido y fosfinita-níquel (0).
- Formación de una especie de dinitrógeno de níquel (Ni) y una especie dinuclear de níquel (Ni) a partir de un precursor de níquel (II).
- Regeneración de la fracción de níquel (II) y formación de un ligando de carbonato de metilo en la reacción de CO2.
Conclusiones:
- Demostró una nueva vía de transformación reversible que involucra al níquel y un ligando a base de fosfuro.
- Se informó de una cooperación no anticipada entre metales y ligandos que impulsó los cambios redox observados.
- Destacó el potencial de los ligandos fosfuro en el diseño de nuevos sistemas catalíticos.
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