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Agrupaciones de iridio-platino de alta nuclealidad: síntesis, estructuras, enlaces y reactividad
Richard D Adams1, Burjor Captain, Michael B Hall
1Department of Chemistry and Biochemistry, USC Nanocenter, University of South Carolina, Columbia, South Carolina 29208, USA. Adams@mail.chem.sc.edu
Journal of the American Chemical Society
|January 20, 2005
Resumen
Este estudio sintetiza nuevos compuestos de clúster de platino e iridio, Ir4 (((CO) 12 [Pt (((PBu ((t) 3) ]2, Ir8 (((CO) 12 [Pt (((PBu ((t) 3) ]4, e Ir6 (((CO) 10 [Pt (((PBu ((t) 3) ]4, revelando estructuras complejas y enlaces. También se formó un nuevo complejo tetrahidrido, Ir6(CO)8[Pt(PBu(t)3)]4(mu-H) 4.
Área de la Ciencia:
- Química organometálica Química orgánica de los metales.
- Química Inorgánica La Química Inorgánica es la química inorgánica.
- Ciencia de los materiales Ciencia de los materiales.
Sus antecedentes:
- Los racimos de carbonilo de iridio son fundamentales en la química organometálica.
- Los complejos de fosfina de platino ofrecen una reactividad y diversidad estructural únicas.
- La exploración de grupos de metales mezclados amplía la comprensión de la unión y la catálisis.
Objetivo del estudio:
- Para sintetizar y caracterizar nuevos grupos de carbonilo de platino-iridio.
- Para investigar la evolución estructural de estos grupos con diferentes condiciones de reacción.
- Para explorar la reactividad de estos grupos, incluida la hidrogenación.
Principales métodos:
- Las reacciones del iridio tetracarbonyl dodecacarbonyl (Ir4(CO) 12) con el bis ((di-tert-butylphosphino) platino ((0) [Pt ((PBu ((t) 3) ].
- Caracterización mediante espectroscopia de Resonancia Magnética Nuclear (RMN) de 1H y 31P.
- Análisis de difracción de rayos X monocristalino para la determinación estructural.
- Los cálculos orbitales moleculares de Fenske-Hall para elucidar el enlace.
Principales resultados:
- Síntesis de Ir4 ((CO) 12 [Pt ((PBu ((t) 3) ]2 a temperatura ambiente, con grupos de Pt que cruzan los bordes de Ir4.
- Formación de racimos de mayor nuclealidad Ir8(CO) 12[Pt(PBu(t) 3)]4 e Ir6(CO) 10[Pt(PBu(t) 3)]4 a temperaturas elevadas.
- Caracterización de un complejo tetrahidrido Ir6(CO) 8[Pt(PBu(t) 3)]4(mu-H) 4 a través de la hidrogenación de Ir6(CO) 10[Pt(PBu(t) 3)]4.
- Los cálculos orbitales moleculares revelaron un enlace Pt-Ir deslocalizado.
Conclusiones:
- El estudio sintetizó con éxito y caracterizó estructuralmente cuatro nuevos grupos de platino-iridio.
- Las condiciones de reacción influyen significativamente en la nucleicidad y la estructura de los grupos resultantes.
- La formación del complejo tetrahidrido demuestra la reactividad de estos sistemas de metales mixtos.
- La unión deslocalizada juega un papel crucial en la estabilidad de estas complejas estructuras organometálicas.
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