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Desaromatización radical única y reducción de dos electrones de un ligando redox-activo

Daniel A Evans¹, Alan H Cowley

¹Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712, United States.

Journal of the American Chemical Society

|September 15, 2012

Resumen

Los investigadores sintetizaron y caracterizaron nuevos ligandos BIAN, incluido un BIAN sustituido por di-tert-butilo (8) y un BIAN sustituido por tert-butilo-hidroxi (9). Estos compuestos se formaron a través de desaromatización radical y vías de reducción.

Área de la Ciencia:

Química organometálica Química orgánica de los metales.
Síntesis de ligandos por síntesis de ligandos.
Química Radical La Química Radical es una ciencia

Sus antecedentes:

El andamiaje del ligando BIAN (bis ((imino) acenafteno) es crucial en la química de la coordinación.
Comprender las modificaciones del ligando BIAN es clave para desarrollar nuevos sistemas catalíticos.
Las vías de dearomatización radical ofrecen rutas únicas a los ligandos funcionalizados.

Objetivo del estudio:

Describir la síntesis y caracterización de nuevos derivados de BIAN.
Investigar las vías radicales de dearomatización y reducción en la funcionalización del ligando BIAN.
Para explorar la formación de di-tert-butilo y tert-butilo-hidroxi sustituido BIAN ligandos.

Principales métodos:

Reacciones radicales de queromatización.
Procesos de reducción de dos electrones.
Estudios de oxidación para la caracterización de ligandos.
Análisis espectroscópico y estructural.

Principales resultados:

Síntesis de [Li(4)][(1,2-di-(tert-butyl) -dpp-BIAN)(2)] (7) a través de la desaromatización radical y la di-tert-butilación.
Formación del diaromatizado ligando 1,2-di-(tert-butilo) -dpp-BIAN (8) a través de la oxidación del compuesto 7.
Aislamiento de un ligando analógico deeroomatizado 1-(tert-butilo)-2-OH-dpp-BIAN (9).

Conclusiones:

El estudio demuestra con éxito una nueva vía de dearomatización radical para la funcionalización del ligando BIAN.
Se sintetizaron y caracterizaron nuevos ligandos BIAN sustituidos por di-tert-butilo y tert-butilo-hidroxi.
Estos hallazgos contribuyen a la comprensión de la reactividad del ligando BIAN y abren vías para el diseño de nuevos ligandos.

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