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Conversión de un disisilazido de zinc a un hidruro de zinc mediado por LiClCl
Debabrata Mukherjee1, Arkady Ellern, Aaron D Sadow
1Department of Chemistry and U.S. Department of Energy Ames Laboratory, Iowa State University, Ames, Iowa 50011, USA.
Journal of the American Chemical Society
|May 18, 2010
Resumen
Una nueva reacción de eliminación beta utilizando zinc (II) y cloruro de litio (LiCl) crea enlaces de silicio-hidrógeno activados. Esta reacción emplea sinérgicamente iones Li(+) y Cl(-) para formar hidruro de zinc y ciclodisilazane.
Área de la Ciencia:
- Química organometálica Química orgánica de los metales.
- Química del silicio Química del silicio
- Coordinación Química de la Coordinación
Sus antecedentes:
- Los compuestos de zinc disilazido son precursores conocidos en la síntesis inorgánica.
- El papel de los haluros de metales alcalinos en la mediación de reacciones de compuestos organometálicos no se entiende completamente.
- La activación de los enlaces Si-H es crucial para el desarrollo de nuevas metodologías sintéticas.
Objetivo del estudio:
- Para investigar una inusual reacción de beta-eliminación que involucra zinc (II) y LiCl.
- Aclarar el papel sinérgico de los iones Li(+) y Cl(-) en el mecanismo de reacción.
- Para caracterizar los productos formados por la reacción de un compuesto de zinc disisilazido con LiCl.
Principales métodos:
- Reacción de un compuesto de zinc disisilazido saturado coordinadamente con LiCl en mezclas THF/tolueno.
- Formación de un adducto que contiene fracciones activadas de SiH.
- Caracterización de los productos de hidruro de zinc y ciclodisilazano resultantes.
Principales resultados:
- Un adducto formado entre LiCl y el compuesto de zinc desisilazido activa las fracciones de SiH.
- El adducto se transforma en hidruro de zinc y ciclodisilazane en THF/tolueno.
- Los iones Li(+) y Cl(-) actúan sinérgicamente, ya que ninguno de los iones por sí solo promueve la eliminación beta.
- La reacción representa una vía formal de eliminación de beta.
Conclusiones:
- La acción sinérgica de Li (((+) y Cl (((-) es esencial para la reacción de eliminación beta observada.
- Este estudio revela una nueva vía de reacción para los compuestos de disilazido de zinc mediados por LiCl.
- Los hallazgos contribuyen a comprender la influencia de los haluros de metales alcalinos en los mecanismos de reacción organometálicos.
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