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Reducción de dos electrones de un nitruro de vanadio (V) por CO para liberar cianato y abrir un sitio de coordinación
Jared S Silvia1, Christopher C Cummins
1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Journal of the American Chemical Society
|December 23, 2008
Resumen
La reacción de un complejo de nitruro terminal con monóxido de carbono produce nitruro de vanadio y cianato de sodio. El estudio también caracteriza los complejos de isocyanato de vanadio y niobio, detallando sus distintas propiedades redox.
Área de la Ciencia:
- Química organometálica Química orgánica de los metales.
- Síntesis Inorgánica y Síntesis Inorgánica.
- La electroquímica es electroquímica.
Sus antecedentes:
- Los complejos de nitruro terminal son intermediarios clave en las reacciones de transferencia de nitrógeno.
- Comprender la reactividad de los nitritos de metales de transición tempranos con moléculas pequeñas es crucial para la catálisis.
- Los complejos de isocianato ofrecen una plataforma para estudiar el comportamiento redox de los ligandos metálicos.
Objetivo del estudio:
- Para investigar la reacción de Na[NV(N[t-Bu]Ar)(3)] con el monóxido de carbono.
- Para sintetizar y caracterizar estructuralmente el complejo de isocyanato (OCN) V (((N[t-Bu]Ar) 3).
- Para comparar la química redox de los complejos de isocianato de vanadio y niobio.
Principales métodos:
- Síntesis de Na[NV(N[t-Bu]Ar)(3)] y posterior reacción con CO.
- Caracterización de los productos de reacción mediante espectroscopia de RMN e IR.
- Síntesis y caracterización estructural de (OCN) V (((N[t-Bu]Ar) ((3) y (OCN) Nb ((N[t-Bu]Ar) ((3).
- Estudios electroquímicos (voltametría cíclica) de los complejos de isocyanato.
Principales resultados:
- Na[NV(N[t-Bu]Ar)(3)] reacciona con el CO para producir V(N[t-Bu]Ar)(3) y cianato de sodio con un rendimiento aislado del 77%.
- La formación de cianato de sodio se confirmó a través de un experimento de etiquetado con (13) C.
- (OCN) V (((N[t-Bu]Ar) ((3) muestra eventos redox a -0.11 V y -1.56 V frente a Fc/Fc (((+).
- (OCN) Nb (((N[t-Bu]Ar) ((3) muestra los eventos redox a -1.1 V y -2.9 V frente a Fc/Fc(+).
Conclusiones:
- La reacción proporciona una ruta sintética para el nitruro de vanadio y el cianato de sodio.
- Se observaron diferencias significativas en los potenciales de reducción entre los complejos de isocyanato de vanadio y niobio.
- Los datos electroquímicos destacan las distintas estructuras electrónicas y actividades redox de estos isocyanatos de metales de transición tempranos.
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