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Interconversión impulsada por hidrógeno y oxígeno entre complejos de dirhodium con puente imido (III) y dirhodium con
Koji Ishiwata1, Shigeki Kuwata, Takao Ikariya
1Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8552, Japan.
Journal of the American Chemical Society
|March 18, 2009
Resumen
Este estudio detalla la síntesis y la reactividad de los complejos de dirhodium (III) sulfonylimido. Estos complejos se someten a la interconversión redox y pueden catalizar reacciones de oxidación aeróbica, mostrando su potencial en la catálisis.
Área de la Ciencia:
- Química organometálica Química orgánica de los metales.
- La catálisis es la catálisis.
- Coordinación Química de la Coordinación
Sus antecedentes:
- Los complejos de dirhodium con ligandos puentes son de interés en la catálisis.
- Los ligandos de sulfonilímido ofrecen propiedades electrónicas y estéricas únicas.
- Comprender el comportamiento redox es crucial para las aplicaciones catalíticas.
Objetivo del estudio:
- Para sintetizar y caracterizar nuevos complejos de dirhodium (III) puenteados con sulfonilímidos.
- Para investigar la reactividad de estos complejos con donantes de hidrógeno y oxígeno.
- Para explorar su potencial como catalizadores en reacciones de oxidación aeróbica.
Principales métodos:
- Síntesis de complejos de dirodio (III) sulfonilímido a través de la reacción con la p-toluenesulfonamida.
- Investigación de la reactividad con donantes de hidrógeno (H2, 2-propanol) y oxígeno.
- Cálculos de DFT y estudios experimentales para aclarar los mecanismos de reacción.
- Pruebas catalíticas para la oxidación aeróbica de H2 y alcoholes.
Principales resultados:
- Formación de un complejo de dirodio con puente sulfonilímido (III) [Cp*Rh) (ii) mu-NTs) (ii) ] (1a).
- Interconversión redox entre los complejos de dirhodium (III) imido y dirhodium (II) amido.
- El complejo 1a demostró actividad catalítica en la oxidación aeróbica de H2 y alcoholes, a diferencia de los complejos relacionados de iridio o rodio sin puentes.
Conclusiones:
- Los complejos de dirodio sintetizados exhiben interesantes propiedades redox y reactividad.
- El ligando sulfonilímido juega un papel clave en la actividad catalítica de estos complejos de dirhodium.
- Estos hallazgos resaltan el potencial de los complejos dinucleares de rodio como catalizadores para la oxidación aeróbica.
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