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The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique
Published on: November 28, 2016
Los complejos [Sn{9}Pt{2}PPh{3}]{2}}- y [Sn{9}Ni{2}CO}{3}- son dos agrupaciones de iones de zintel de metal de
Banu Kesanli1, James Fettinger, Donna R Gardner
1Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USA.
Journal of the American Chemical Society
|April 25, 2002
Resumen
Se sintetizaron nuevos grupos de estaño-platino y estaño-níquel. Estos nuevos grupos exhiben propiedades estructurales y electrónicas únicas, incluido el comportamiento fluxional en solución y la activación de C-H durante la síntesis.
Área de la Ciencia:
- Química Inorgánica La Química Inorgánica es la química inorgánica.
- Química organometálica Química orgánica de los metales.
- Ciencia de los materiales Ciencia de los materiales.
Sus antecedentes:
- Los clústeres a base de estaño son de interés debido a sus estructuras electrónicas únicas y aplicaciones potenciales.
- La síntesis de grupos polianiónicos complejos a menudo requiere condiciones de reacción específicas y agentes estabilizadores.
Objetivo del estudio:
- Para sintetizar y caracterizar nuevos grupos de estaño-platino y estaño-níquel.
- Investigar las propiedades estructurales, electrónicas y dinámicas de estos nuevos compuestos de racimo.
- Para explorar los mecanismos de reacción involucrados en la formación de estos grupos.
Principales métodos:
- Síntesis de grupos de estaño utilizando estanidos de metales alcalinos (K4Sn9) y precursores de metales de transición (Pt, Ni).
- Caracterización mediante difracción de rayos X, espectroscopia de RMN (119Sn, 31P, 195Pt), espectroscopia de EPR y ESI-MS.
- El etiquetado de deuterio y los experimentos de captura de hidrogenación para estudiar los mecanismos de reacción.
Principales resultados:
- Síntesis de [Sn{9}Pt{2}PPh{3}]2- (2), un grupo hiperclásico de 10 vértices con simetría C3v, formado por la activación C-H del disolvente.
- Síntesis de [Sn{9}Ni{2}CO}]3- (3), un closo de 10 vértices con simetría C4v, que exhibe paramagnetismo y interacciones hiperfinas.
- El grupo 2 muestra un comportamiento fluxional en solución, con un intercambio intramolecular consistente con una varilla Pt-Pt-PPh3 rígida.
- El análisis de ESI-MS confirmó la formación de iones padres y varias especies relacionadas para ambos grupos.
Conclusiones:
- Se han sintetizado con éxito nuevos grupos de metales de transición de estaño con distintas propiedades estructurales y electrónicas.
- La formación del grupo estaño-platino implica una doble vía de activación C-H.
- El comportamiento fluxional del cúmulo estaño-platino proporciona información sobre los procesos dinámicos en los cúmulos polianiónicos.
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