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La formación de enlaces C-C reversibles entre los ligandos de piridina redox-activos en los complejos de hierro
Thomas R Dugan1, Eckhard Bill, K Cory MacLeod
1Department of Chemistry, University of Rochester, Rochester, New York, USA.
Journal of the American Chemical Society
|November 28, 2012
Resumen
Este estudio revela complejos de hierro donde los ligandos de piridina ganan densidad de espín, actuando como depósitos de electrones. Estos ligandos se someten a la formación de enlaces C-C reversibles, almacenando electrones y permitiendo una química única del hierro.
Área de la Ciencia:
- Química organometálica Química orgánica de los metales.
- Química Inorgánica La Química Inorgánica es la química inorgánica.
- Coordinación Química de la Coordinación
Sus antecedentes:
- Los complejos de hierro con ligandos voluminosos ofrecen una reactividad única.
- La comprensión de la distribución de electrones en los sistemas de metal-ligando es crucial para la catálisis.
- Los ligandos de piridina pueden participar en los procesos redox.
Objetivo del estudio:
- Para sintetizar y caracterizar nuevos complejos de hierro.
- Para investigar la estructura electrónica y la distribución de la densidad de espín en estos complejos.
- Para explorar la reactividad de los ligandos de piridina coordinados.
Principales métodos:
- Síntesis de los complejos L(Me) Fe (((Py-R) ((2).
- Análisis estructural a través de la cristalografía de rayos X.
- Caracterización espectroscópica (por ejemplo, EPR, Mössbauer).
- Cálculos de la Teoría Funcional de la Densidad (DFT).
Principales resultados:
- Se sintetizaron complejos de hierro (I) con ligandos de beta-diketiminato voluminosos.
- Los ligandos de piridina aceptan preferentemente la densidad de espín sin emparejar.
- La especie S = 3/2 es un híbrido de resonancia de Fe (II) / piridina y Fe (I).
- Las piridinas desprotegidas se someten a un acoplamiento radical reversible (formación de enlaces C-C).
- Un complejo acoplado de diirón ((II) almacena electrones como un enlace C-C en el ligando.
Conclusiones:
- El almacenamiento de electrones en los ligandos a través de la formación de enlaces C-C proporciona un nuevo paradigma para los ligandos redox-activos.
- Esta formación reversible de enlaces C-C en los ligandos de piridina es una característica clave de estos complejos de hierro.
- Los hallazgos ofrecen información sobre los mecanismos de transferencia de electrones y las posibles aplicaciones en la catálisis.
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