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Resolución fotoquímica de un complejo termalmente inerte de Ru (phbpy) (N-N) (Sulfoxide)
Lucien N Lameijer1, Corjan van de Griend1, Samantha L Hopkins1
1Leiden Institute of Chemistry, Leiden University , Einsteinweg 55 , 2333CC Leiden , The Netherlands.
Journal of the American Chemical Society
|December 12, 2018
Resumen
Este estudio introduce un nuevo método de fotosubstitución para el aislamiento de complejos quirales de rutenio organometálico. Esta estrategia fotoquímica permite la separación de diastereoisómeros, ofreciendo una nueva ruta sintética para la síntesis de complejos quirales.
Área de la Ciencia:
- Química organometálica
- La fotoquímica
- Síntesis quiral
Sus antecedentes:
- Los complejos organometálicos quirales son cruciales en la catálisis y la ciencia de los materiales.
- Los métodos tradicionales para resolver complejos quirales, como el intercambio térmico de ligandos, a menudo son ineficaces debido a la inercia del enlace.
- Los complejos ciclometalizados de rutenio (II) con ligandos fenil-bipiridil presentan propiedades estructurales y fotoquímicas únicas.
Objetivo del estudio:
- Desarrollar una estrategia de fotosubstitución para el aislamiento de complejos organometálicos quirales.
- Sintetizar y caracterizar una serie de complejos quirales de rutenio metalizado.
- Investigar el comportamiento fotoquímico de estos complejos y comprender los factores que influyen en la fotosubstitución.
Principales métodos:
- Síntesis y caracterización de cinco complejos de rutenio ((II) ciclometalizados: Ru ((phbpy) ((N-N) ((DMSO-κS)) ((PF6).
- Reacciones de fotosubstitución inducidas por la irradiación de luz visible en el acetonitrilo.
- Resolución quiral mediante coordinación térmica de un sulfóxido quiral seguido de la separación de diastereoisómeros mediante HPLC en fase inversa.
Principales resultados:
- Tres de los cinco complejos sintetizados ([1]PF6-[3]PF6) se sometieron a fotosubstituación selectiva.
- La resolución quiral de los diastereoisómeros se logró con éxito para un complejo específico mediante métodos fotoquímicos.
- Los análisis fotoquímicos, electroquímicos y orbitales de frontera explicaron la variación de la inercia fotoquímica entre los complejos.
Conclusiones:
- La fotosubstitución ofrece una alternativa viable a los métodos térmicos para resolver los complejos organometálicos quirales.
- Este enfoque fotoquímico proporciona una nueva vía para la síntesis de complejos de rutenio metalizado enantioméricamente puros.
- La comprensión de los factores electrónicos y estructurales que rigen la fotosubstitución es clave para diseñar nuevos complejos quirales.
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