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Activación de dióxido de oxígeno por un dihidruro de osmio: preparación y caracterización de un complejo plano

Miguel A Esteruelas¹, Francisco J Modrego, Enrique Oñate

¹Departamento de Química Inorgánica-Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-Consejo Superior de Investigaciones Científicas, 50009-Zaragoza, Spain. maester@posta.unizar.es

Journal of the American Chemical Society

|October 30, 2003

Resumen

Los compuestos de osmio OsH2Cl2(PiPr3)2 reaccionan con el oxígeno para formar las especies dioxo Os(VI). Una reducción adicional da como resultado un raro compuesto dioxo Os(IV), que muestra una nueva activación de enlace O=O y una química plana cuadrada d4.

Área de la Ciencia:

Química organometálica Química orgánica de los metales.
Química Inorgánica La Química Inorgánica es la química inorgánica.
La catálisis por osmio.

Sus antecedentes:

Los complejos de osmio son conocidos por su diversa reactividad.
La activación directa del enlace doble O=O en el dioxígeno es una transformación desafiante pero crucial en química.
Los complejos metálicos d4 cuadrados-planos son relativamente raros y exhiben propiedades electrónicas únicas.

Objetivo del estudio:

Para investigar la reacción de OsH2Cl2(PiPr3)2 con el oxígeno molecular.
Para sintetizar y caracterizar nuevas especies de osmium dioxo.
Explorar la reducción de los complejos dioxo Os(VI) a sus análogos Os(IV).

Principales métodos:

Exposición de OsH2Cl2(PiPr3)2 al aire y al oxígeno puro.
Reacción de las especies dioxo Os(VI) con el n-butilitio (n-BuLi).
Caracterización de los compuestos de osmio resultantes.

Principales resultados:

Se logró la activación directa del doble enlace O=O, dando el compuesto dioxo OsO2Cl2PiPr3)2.2.
La reducción de las especies de Os(VI) con n-BuLi proporcionó el nuevo derivado dioxo de Os(IV) OsO2(PiPr3)2.2.
El producto Os (IV) representa un raro ejemplo de un complejo plano-cuadrado d4.

Conclusiones:

OsH2Cl2(PiPr3)2 se somete fácilmente a la activación directa del enlace O=O con el oxígeno.
Se sintetizó un nuevo complejo dioxo Os(IV), OsO2(PiPr3) 2, que resalta una rara geometría plana cuadrada d4.
Este estudio amplía la comprensión de la reactividad del osmio y la síntesis de estados de oxidación y geometrías inusuales.

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