Complejos de rutenio de C,C'-bis(etinile) carboranos: una investigación de las interacciones electrónicas mediadas por espaciadores pseudo-aromáticos esféricos
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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Mark A Fox1, Rachel L Roberts, Thomas E Baines
1Department of Chemistry, Durham University, South Rd, Durham, DH1 3LE, UK.
Journal of the American Chemical Society
|February 26, 2008
Resumen
Este estudio detalla nuevos complejos rutenio-acetiluro con carboranos. Los complejos bimetálicos muestran estados estabilizados de valencia mixta debido a las interacciones metal-metal, confirmados por espectroscopia y cálculos de DFT.
Área de la Ciencia:
- Química organometálica Química orgánica de los metales.
- Coordinación Química de la Coordinación
- Química del carborano Química del carborano
Sus antecedentes:
- Los complejos rutenio-acetiluro son valiosos en la catálisis y la ciencia de los materiales.
- Los carboranos ofrecen propiedades electrónicas y estructurales únicas cuando se incorporan a los ligandos.
- Comprender el comportamiento redox en sistemas bimetálicos es crucial para el diseño de moléculas funcionales.
Objetivo del estudio:
- Sintetizar y caracterizar estructuralmente nuevos complejos mono y bimetálicos de rutenio-acetiluro con carboranos.
- Para investigar las propiedades espectroscópicas y electroquímicas de estos complejos en varios estados redox.
- Para dilucidar la estructura electrónica y los mecanismos de estabilización de los estados de valencia mixta en sistemas bimetálicos.
Principales métodos:
- Síntesis y caracterización estructural de complejos monometálicos y bimetálicos de rutenio-acetiluro-carborano.
- Análisis espectroscópico que incluye espectroscopia UV-NIR e IR a través de estados redox accesibles.
- Estudios electroquímicos utilizando voltametría cíclica.
- Cálculos de la Teoría Funcional de Densidad (DFT) en sistemas modelo.
Principales resultados:
- Se ha conseguido la preparación y caracterización de cuatro nuevos complejos de rutenio: [Ru(1-CC-1,10-C2B8H9) (((dppe)Cp*] (3a), [Ru(1-CC-1,12-C2B10H11) (((dppe)Cp*] (3b), [{Ru((dppe)Cp*}2{μ-1,10-(CC)2-1,10-C2B8H8}] (4a), y [{Ru(dppe)Cp*}2{μ-1,12-(CC)2-1,12-C2B10H10}] (4b).
- Los complejos bimetálicos (4a, 4b) exhiben ondas anódicas de un electrón bien separadas, lo que indica la estabilización de las especies monocationales intermedias.
- La estabilización se atribuye a las interacciones metal-metal a través de ~12.5 Å, lo que lleva a compuestos de valencia mixta localizados por valencia (clase II).
- Los complejos bimetálicos monooxidados muestran una banda de absorción electrónica de baja energía característica que indica una transición de transferencia de carga de intervalo (IVCT).
- Los cálculos de DFT apoyan los datos espectroscópicos observados y las estructuras electrónicas localizadas de los cationes de valencia mixta.
Conclusiones:
- El estudio sintetizó y caracterizó con éxito nuevos complejos rutenio-acetiluro-carborano.
- Las interacciones metal-metal de largo alcance estabilizan significativamente los estados de valencia mixta en los sistemas bimetálicos.
- Estos hallazgos proporcionan información sobre la comunicación electrónica y el comportamiento redox de compuestos organometálicos complejos.
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