Un ejemplo de unión de O2 en un sistema de corroles de cobalto (II) y complejos cobalto-ciano y cobalto-alquinilo de alta valencia
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High-pressure Sapphire Cell for Phase Equilibria Measurements of CO2/Organic/Water Systems
Published on: January 24, 2014
Bobby Ramdhanie1, Joshua Telser, Andrea Caneschi
1Department of Chemistry, Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218, USA.
Journal of the American Chemical Society
|February 26, 2004
Resumen
Se sintetizaron y estudiaron nuevos complejos de corrolazina de cobalto. La investigación detalla el cobalto.
Área de la Ciencia:
- * Química Inorgánica y Química Inorgánica.
- * Química Organometálica es una especialidad de la química organometálica.
- * Espectroscopia con espectroscopía.
Sus antecedentes:
- * Los ligandos de la corrolazina son de interés para estabilizar estados de oxidación altos en complejos metálicos.
- * Comprender las configuraciones electrónicas y la reactividad de las corrolazinas de cobalto es crucial.
Objetivo del estudio:
- * Para sintetizar y caracterizar nuevos complejos de corrolazina (Cz) de cobalto.
- * Investigar el papel de los ligandos de la corrolazina en la estabilización de los altos estados de oxidación del cobalto.
- * Para explorar las capacidades de unión al dioxígeno de los complejos de cobalto reducido (II) corrolazina.
Principales métodos:
- * Síntesis de complejos de corrolazina de cobalto.
- * Cristalografía de rayos X para la determinación estructural.
- * Técnicas espectroscópicas (por ejemplo, EPR) para el análisis de la configuración electrónica.
- * Generación in situ y caracterización de complejos de cobalto (II).
- * Espectroscopia de resonancia paramagnética de electrones (VT-EPR) de temperatura variable.
Principales resultados:
- * Se sintetizaron dos nuevos complejos de corrolazina de cobalto, (TBP) ((8) CzCoCN (1) y (TBP) ((8) CzCo ((CCSiPh ((3)) (2)).
- * El complejo 2 exhibió un enlace Co-C corto y apilamiento pi intermolecular.
- * El complejo 1 fue identificado como un radical picativo de cobalto, mientras que el complejo 2 es un híbrido de resonancia de cobalto y cobalto.
- * Se generó un complejo reducido de cobalto (II), (TBP) (CzCo) (II) (py) (-), y se demostró que se une de manera reversible al dioxígeno.
- * El adducto de dioxígeno formó un complejo cobalto-superoxo estable, observado a través de la espectroscopia EPR hasta 240 K.
Conclusiones:
- * Los ligandos de corrolazina estabilizan efectivamente los estados de oxidación alta en los complejos de cobalto.
- * El estudio proporciona la primera observación de la unión del dioxígeno a un complejo de cobalto (II) corróleo.
- * El complejo cobalto-superoxo caracterizado demuestra el potencial de estos sistemas en la química relacionada con el oxígeno.
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