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Preparación anódica de [Re2Cp2(CO)6]2+: una dicción dimérica que proporciona el poderoso oxidante de un electrón

Daesung Chong¹, Ayman Nafady, Paulo Jorge Costa

¹Department of Chemistry, University of Vermont, Burlington, Vermont 05405, USA.

Journal of the American Chemical Society

|November 10, 2005

Resumen

Los compuestos de renio de medio sándwich de piano y taburete se oxidan a cationes Re (II) de 17 electrones persistentes. Estos cationes forman dicciones diméricas estables a través de un enlace Re-Re, lo que permite su aislamiento y uso como oxidantes fuertes.

Área de la Ciencia:

Química organometálica Química orgánica de los metales.
La electroquímica es electroquímica.
Química computacional es la química computacional.

Sus antecedentes:

Los compuestos piano-sábana de medio sándwich, específicamente Re (((η5-C5R5) (((CO) 3 (1, R = H; 2, R = Me), son importantes en la química organometálica.
Comprender el comportamiento electroquímico y la estabilidad de los complejos metálicos oxidados es crucial para el desarrollo de nuevas metodologías sintéticas.

Objetivo del estudio:

Para oxidar electroquímicamente los compuestos de renio de medio sándwich piano-sábana a sus correspondientes cationes Re (II) de 17 electrones.
Investigar la estabilidad y la reactividad de estos radicales cationes en solución y en estado sólido.
Explorar el potencial de estas especies oxidadas como fuertes oxidantes de un electrón.

Principales métodos:

Oxidación anódica de compuestos de renio en electrodos de carbono vidrioso en CH2Cl2/[Bu4N][B(C6F5) 4].
Mediciones electroquímicas, incluida la voltametría cíclica, para determinar los potenciales redox (E1⁄2).
Cálculos de la Teoría Funcional de Densidad (DFT) para dilucidar la estructura electrónica y el enlace en las especies oxidadas.
Electroquímica anódica preparativa para el aislamiento de sales puras.

Principales resultados:

Los compuestos Re (η5-C5R5) (CO) 3 se oxidaron con éxito a cationes Re (II) de 17 electrones persistentes con altos potenciales redox positivos.
Los cationes radicales existen en equilibrio con las dications diméricas, estabilizadas por un largo enlace Re-Re (≈3.3 Å) formado a través de la rehíbridación orbital metal-ligando.
Se aislaron sales puras, [1][B(C6F5)4]2 y [2][B(C6F5)4]2, lo que demuestra la estabilidad de las formas oxidadas.
La sal aislada [1][B(C6F5)4]2 sirve como una forma de almacenamiento estable para el potente oxidante de un electrón [1]+.

Conclusiones:

La oxidación de un electrón de los complejos de renio piano-sábana de medio sándwich produce cationes Re (II) de 17 electrones persistentes.
La dimerización a través de un enlace Re-Re es un mecanismo de estabilización clave para estas especies altamente oxidadas.
La electroquímica preparatoria proporciona una ruta viable para aislar y utilizar estos fuertes oxidantes de un electrón en la síntesis.

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