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La división y la funcionalización del dinitrógeno en la esfera de coordinación del renio

Isabel Klopsch¹, Markus Finger, Christian Würtele

¹Institut für Anorganische Chemie, Georg-August-Universität , Tammannstraße 4, 37077 Göttingen, Germany.

Journal of the American Chemical Society

|May 1, 2014

Resumen

Los investigadores sintetizaron un nuevo complejo de renio (III) que divide el dinitrógeno (N2) tras la reducción. Este proceso produce un nitruro de renio ((V) único, marcando una primicia en la química de coordinación del renio y permitiendo la posterior formación de enlaces C-N.

Área de la Ciencia:

Química Inorgánica La Química Inorgánica es la química inorgánica.
Química organometálica Química orgánica de los metales.
Coordinación Química de la Coordinación

Sus antecedentes:

Los complejos de renio son explorados para aplicaciones catalíticas.
La fijación de nitrógeno sigue siendo un desafío importante en la química.
Los ligandos de pinza ofrecen entornos de coordinación únicos.

Objetivo del estudio:

Para sintetizar un nuevo complejo de renio (III) con un ligando de pinza.
Para investigar la reactividad del complejo de renio hacia la escisión del dinitrógeno (N2).
Para demostrar la funcionalización de un ligando de nitruro derivado de N2.

Principales métodos:

Reacción de [ReCl3 (((PPh3) 2 ((NCMe)) ] con el ligando de pinza HN (((CH2CH2PtBu2) 2 (HPNP).
Reducción del complejo de renio (III) resultante para dividir el N2.2.
Caracterización del complejo de nitruro de renio ((V).
Funcionalización del ligando del nitruro utilizando el MeOTf.

Principales resultados:

Formación del complejo de cinco coordenadas de renio ((III) [ReCl2 ((PNP) ].
Cleavage de N2 durante la reducción para producir el complejo de nitruro de renio (V) [Re (N) Cl (PNP) ], el primer ejemplo de este tipo para el renio.
Demostración de la formación selectiva de enlaces C-N en el ligando nitruro.

Conclusiones:

Se ha establecido una nueva vía para la activación y funcionalización de N2 utilizando renio.
El complejo de nitruro de renio sintetizado es un intermediario clave para las transformaciones basadas en nitrógeno.
Este trabajo abre caminos para el desarrollo de nuevos procesos catalíticos que involucran nitrógeno.

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