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La activación de C-H por un complejo diselenido dinickel (II)
Jessica Wallick1, Charles G Riordan, Glenn P A Yap
1Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
Journal of the American Chemical Society
|September 27, 2013
Resumen
La adición de selenio a un complejo de níquel (I) forma un complejo de diníquel (II) deselenido. Este complejo puede oxidar sustratos y convertir entre formas de selenio, mostrando la química dinámica del selenio en complejos de níquel.
Área de la Ciencia:
- Química Inorgánica La química inorgánica es la química inorgánica.
- Química organometálica Química orgánica de los metales.
- Coordinación Química de la Coordinación
Sus antecedentes:
- Los complejos de níquel son catalizadores versátiles en varias transformaciones químicas.
- Los ligandos de selenio juegan un papel crucial en los sistemas biológicos y en la catálisis inorgánica.
- Comprender la reactividad de los complejos metálicos que contienen selenio es clave para desarrollar nuevos procesos catalíticos.
Objetivo del estudio:
- Para sintetizar y caracterizar un nuevo complejo dinickel (II) diselenido.
- Para investigar el comportamiento redox y la reactividad del complejo sintetizado.
- Para explorar el potencial de este complejo en la oxidación del sustrato y las reacciones de transferencia de selenio.
Principales métodos:
- Síntesis del complejo precursor del níquel (I) [Ni (Me) 4 (aneN4) (CO) ]PF6.6.
- Reacción redox con el selenio elemental para formar el complejo dinickel (II) diselenido.
- Cristalografía de rayos X para determinar la estructura del complejo diselenido.
- Reacciones de oxidación con 9,10-dihidroantraceno y 1,4-ciclohexadieno.
- Caracterización del complejo de hidroselenida resultante y su conversión de nuevo al deselenido adduct.
Principales resultados:
- La adición de selenio a [Ni(Me4[12]aneN4)(CO) ]PF6 produjo el complejo dinickel(II) diselenido {[Ni(Me4[12]aneN4)]2(Se2)}(PF6)2 con un rendimiento del 70%.
- La estructura cristalina reveló un ligando μ-η(2):η(2)-Se2 con una longitud de enlace Se-Se de 2.379(13) Å.
- El complejo dinickel (II) diselenido se oxidó 9,10-dihidroantraceno y 1,4-ciclohexadieno al calentarse, formando el complejo hidroselenido terminal [Ni (Me4) [12]aneN (SeH) ]PF6.6.
- El complejo de hidroselenida fue regenerado al complejo de diselenido por reacción con un radical fenoxi.
Conclusiones:
- Se sintetizó y caracterizó estructuralmente con éxito un nuevo complejo de dinickel (II) diselenido.
- El complejo exhibe un comportamiento redox dinámico, facilitando la oxidación del sustrato y la transferencia de selenio.
- Este estudio pone de relieve el potencial de los complejos de níquel-selenio en aplicaciones catalíticas que involucran procesos redox y química del selenio.
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