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Isomerización homeomórfica como elemento de diseño en moléculas de contenedores; Enlace, desplazamiento y transporte
Sugam Kharel1, Hemant Joshi1, Stephen Bierschenk1
1Department of Chemistry, Texas A&M University , P.O. Box 30012, College Station, Texas 77842-3012, United States.
Journal of the American Chemical Society
|January 12, 2017
Resumen
Un nuevo ligando de difosfina facilita el transporte eficiente de dicloruros metálicos (MCl2) entre las fases acuosa y orgánica. Este proceso se mejora significativamente mediante el uso de cianuro de potasio, lo que permite la recuperación selectiva de metales.
Área de la Ciencia:
- Química organometálica
- Química de coordinación
- Ciencias de los materiales
Sus antecedentes:
- Las difosfinas de cabeza de puente exhiben una isomerización homeomórfica única.
- Los pares aislados de isómeros externos pueden coordinarse con los dicloruros de metales ácidos de Lewis (MCl2).
- Los aductos en forma de jaula se forman con MCl2 (M = Pt, Pd, Ni).
Objetivo del estudio:
- Investigar las capacidades de transporte de un ligando de difosfina de cabeza de puente para dicloruros metálicos.
- Explorar la influencia de las condiciones de transferencia de fase y de los aditivos en la eficiencia del transporte de metales.
- Para comparar las velocidades de transporte de los diferentes dicloruros metálicos.
Principales métodos:
- Isomerización homeomórfica de la difosfina de cabeza de puente ((CH2) 14) 3P.
- Formación de aductos tipo jaula con MCl2.
- Experimentos de extracción líquido-líquido en tubo U para el transporte de metales.
- Estudios de transferencia de fase con diclorometano y soluciones acuosas.
- Análisis de la cinética del transporte de metales y de las relaciones de equilibrio.
Principales resultados:
- El ligando de difosfina elimina efectivamente el MCl2, formando adutos estables.
- Se logra el transporte de dicloruro metálico a través de fases, con un equilibrio influenciado por aditivos como el KCN.
- El cianuro de potasio acelera significativamente el transporte y mejora las relaciones de equilibrio.
- El transporte de cloruro de paladio (PdCl2) es más rápido que el de cloruro de platino (PtCl2) en sistemas mixtos.
- Un análogo de cadena más larga, P (((CH2) 18) 3P, muestra una eficacia similar.
Conclusiones:
- Las difosfinas de cabeza de puente son ligandos efectivos para el transporte de MCl2 entre fases inmiscibles.
- El uso del KCN como aditivo mejora considerablemente la eficiencia y la selectividad del transporte.
- Este sistema ofrece un método prometedor para la recuperación y separación selectiva de metales.
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