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Un complejo de cerio imido cubierto de metal alcalino

Lukman A Solola¹, Alexander V Zabula¹, Walter L Dorfner¹

¹P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.

Journal of the American Chemical Society

|May 11, 2016

Resumen

Los investigadores sintetizaron el primer enlace múltiple terminal de cerio-nitrógeno utilizando una nueva estrategia de ligando. Este avance proporciona un enlace cerio-nitrógeno estable y altamente reactivo, el más corto conocido, avanzando en la química de los lantánidos.

Área de la Ciencia:

Química organometálica
Química de los lantánidos
Síntesis inorgánica

Sus antecedentes:

Los enlaces múltiples de los ligandos de lantánidos terminales son excepcionalmente raros debido a la alta reactividad esperada y a la escasa superposición orbital.
Las estrategias anteriores lucharon por aislar estas especies debido a la polarización de carga e inestabilidad.

Objetivo del estudio:

Desarrollar una nueva estrategia para el aislamiento de enlaces múltiples terminales de lantanuro-ligando.
Sintetizar y caracterizar un complejo terminal de enlaces múltiples de cerio y nitrógeno.

Principales métodos:

Se utilizó un marco de ligando tris ((hidroxilaminato), TriNOx ((3-), para la protección estérica y electrónica.
Complejos de cerio (IV) utilizados en la síntesis.
Caracterizó el complejo resultante utilizando cristalografía de rayos X.

Principales resultados:

Se aisló con éxito el primer enlace múltiple terminal de cerio-nitrógeno (CeN).
El complejo sintetizado, [K(DME) ], exhibe la longitud de enlace CeN más corta conocida a 2.119 ((3) Å.
El marco de ligandos TriNOx3- impidió la mezcla de ligandos, la oligomerización y la reducción.

Conclusiones:

La estrategia desarrollada utilizando el cerio ((IV) y el ligando TriNOx ((3-) es efectiva para aislar enlaces múltiples terminales de lantánido-ligando.
Este trabajo expande la química conocida de los lantánidos, demostrando la viabilidad de estabilizar enlaces múltiples altamente reactivos.

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