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Síntesis de un nitruro de hafnio libre de bases a partir de la escisión de N2: una plataforma versátil para la

Scott P Semproni¹, Paul J Chirik

¹Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.

Journal of the American Chemical Society

|July 9, 2013

Resumen

Este estudio introduce un nuevo complejo de hafnio que puede sintetizar moléculas orgánicas a partir de nitrógeno y monóxido de carbono. Esta plataforma versátil permite nuevas transformaciones químicas utilizando materiales de partida fácilmente disponibles.

Área de la Ciencia:

Química organometálica Química orgánica de los metales.
Síntesis Inorgánica y Síntesis Inorgánica.
La catálisis de la catálisis.

Sus antecedentes:

Los complejos organometálicos metastables ofrecen una reactividad única.
La escisión del dinitrógeno es una transformación desafiante pero importante.
Los complejos de hafnio se exploran cada vez más para nuevas reacciones químicas.

Objetivo del estudio:

Para sintetizar y caracterizar un complejo de dihafnoceno μ-nitrido libre de bases.
Para explorar la reactividad de este complejo en la formación de enlaces N-C.
Para establecer su utilidad como plataforma para la síntesis de moléculas orgánicas.

Principales métodos:

Síntesis de un complejo de dihafnoceno μ-nitrido a través de la escisión de dinitrógeno inducida por CO.
Reacciones con alquinos, nitriles, CO2 y isocyanatos.
Caracterización mediante técnicas espectroscópicas y analíticas.

Principales resultados:

Formación de ligandos sustituidos de cianamida, tipo amidinato y ureato.
La desoxigenación del CO2 y la formación de ligandos de isocyanato.
Isomerización de los ligandos de ureato a las carbodiimidas puentes.
Demostración de la transferencia de grupos entre los centros de hafnio.

Conclusiones:

El complejo dihafnoceno μ-nitrido libre de bases es una plataforma versátil.
Permite la síntesis de diversas moléculas orgánicas a partir de N2 y CO.
Este trabajo amplía la utilidad sintética de la química del organohafnio.

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