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Los complejos de hierro dinitrosil relevantes para la nitrosilación del racimo de Rieske
Zachary J Tonzetich1, Loi H Do, Stephen J Lippard
1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Journal of the American Chemical Society
|May 23, 2009
Resumen
La reacción de un modelo de racimo de Rieske con el óxido nítrico desmonta el núcleo de hierro y azufre, formando complejos dinitrosilíricos (DNIC). Se sintetizaron nuevos DNIC neutrales y reducidos, ofreciendo raros ejemplos de socios redox.
Área de la Ciencia:
- Química bioorgánica Química bioorgánica.
- Coordinación Química de la Coordinación
- Química del óxido nítrico Química del óxido nítrico
Sus antecedentes:
- Los racimos de Rieske son proteínas vitales de hierro y azufre.
- El óxido nítrico (NO) desempeña diversas funciones biológicas.
- Los complejos de dinitrosilirón (DNIC) están implicados en la señalización de NO.
Objetivo del estudio:
- Para investigar la reacción de un modelo de racimo de Rieske sintético con óxido nítrico.
- Para sintetizar y caracterizar nuevos complejos de dinitrosilirón (DNIC).
- Para explorar el comportamiento redox de los DNIC en un entorno rico en nitrógeno.
Principales métodos:
- Reacción de un modelo específico de racimo de hierro-azufre con óxido nítrico.
- Aislamiento y caracterización de complejos de dinitrosilirón (DNIC) utilizando técnicas como la cristalografía de rayos X (implicado).
- Síntesis y reducción electroquímica de un nuevo DNIC ligado al beta-diketiminato.
Principales resultados:
- El óxido nítrico indujo el desmontaje del núcleo de hierro y azufre, formando complejos dinitrosilíricos (DNIC).
- Se aisló y caracterizó un nuevo DNIC, (Et4) N) [N2CHPh) Fe (NO) 2].
- Se sintetizó un DNIC neutro {Fe(NO) ((2))) ((9) con un ligando beta-diketiminato, y su reducción de un electrón produjo un DNIC {Fe(NO) ((2))) ((10) aislable.
Conclusiones:
- El modelo de racimo de Rieske sintético muestra homología con racimos de Fe ((2) S ((2)) ligados puramente al tiolato en reacciones NO.
- Se prepararon socios redox DNIC estructuralmente análogos, lo que representa un ejemplo raro.
- Estos hallazgos avanzan en la comprensión de la reactividad del grupo de hierro-azufre y la química del complejo dinitrosilirón.
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