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Caracterización de los iones silicio sustituidos por hidrógeno en la fase condensada
Qian Wu1, Elisabeth Irran1, Robert Müller1
1Institut für Chemie, Technische Universität Berlin, 10623 Berlin, Germany.
Science (New York, N.Y.)
|July 13, 2019
Resumen
Los investigadores sintetizaron iones de silicio sustituidos por hidrógeno mediante una nueva estrategia de protólisis. Este método proporciona acceso a varios cationes de silicio, incluidos los iones tris (tert-butilo) sililo e hidruro de silicio, cruciales para comprender la química del silicio.
Área de la Ciencia:
- Química del silicio orgánico
- Química del carbocatión
- Química de los elementos del grupo principal
Sus antecedentes:
- Los iones de silicio sustituidos por hidrógeno son especies altamente reactivas y buscadas en la química del silicio.
- Los estudios anteriores se han enfrentado a desafíos en el aislamiento y la caracterización de estos intermedios transitorios.
- El desarrollo de estrategias de estabilización es crucial para estudiar sus propiedades fundamentales.
Objetivo del estudio:
- Desarrollar un método fiable para sintetizar una serie completa de iones de silicio sustituidos por hidrógeno.
- Investigar las propiedades estructurales y electrónicas de estos cationes de silicio.
- Comprender el papel de los sustituyentes voluminosos y los contraiones en la estabilización de las especies reactivas de silicio.
Principales métodos:
- Se utilizó una estrategia de protólisis que empleaba un ácido carborano (CHB11H5Br6-).
- Se realizó la escisión quimioselectiva de los enlaces Si-C ((sp2) o Si-H.
- El análisis cristalográfico se utilizó para determinar las estructuras moleculares de los iones de silicio sintetizados.
Principales resultados:
- Se logró el acceso a la serie completa de [CHB11H5Br6] - estabilizado R2SiH +, RSiH2 + y SiH3 + cationes.
- Los grupos tert-butilo voluminosos en el silicio eran esenciales para evitar la redistribución del sustituto.
- Los datos cristalográficos revelaron piramidalización en el átomo de silicio en cationes R2SiH+ y RSiH2+, en contraste con la estructura trigonal-planar de SiH3+.
Conclusiones:
- La estrategia de protólisis desarrollada ofrece una ruta robusta para diversos iones de silicio sustituidos por hidrógeno.
- La diversidad estructural observada (piramidal frente al silicio plano) pone de relieve la influencia de los sustituyentes y los contrarios.
- Este trabajo proporciona información fundamental sobre la química y las preferencias estructurales de los cationes de silicio.
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