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Reacción de transferencia de oxo de un complejo de bis (mu-oxo) dicobre (III) a los sulfuros

Masayasu Taki¹, Shinobu Itoh, Shunichi Fukuzumi

¹Department of Chemistry, Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan.

Journal of the American Chemical Society

|February 7, 2002

Resumen

Este estudio demuestra la primera oxigenación exitosa de sulfuros a sulfóxidos utilizando un nuevo complejo bis (mu-oxo) dicopro (III). La reacción procede a través de un mecanismo de dos pasos que involucra la asociación del sustrato y la transferencia intramolecular de átomos de oxígeno.

Área de la Ciencia:

Química Inorgánica La Química Inorgánica es la química inorgánica.
Síntesis orgánica La síntesis orgánica.
La catálisis es la catálisis.

Sus antecedentes:

Los sulfuros son compuestos orgánicos importantes, y su oxidación a sulfóxidos es una transformación clave en la síntesis.
Los complejos de cobre son catalizadores conocidos para varias reacciones de oxidación.
El desarrollo de catalizadores de oxidación eficientes y selectivos sigue siendo un desafío importante en la química.

Objetivo del estudio:

Para lograr la oxigenación directa de sulfuros a sulfóxidos utilizando un nuevo complejo bis (mu-oxo) dicopro (III).
Para dilucidar el mecanismo de reacción a través de un análisis cinético detallado.
Investigar el papel del ligando de soporte en el proceso catalítico.

Principales métodos:

Síntesis de un nuevo complejo bis ((mu-oxo) dicopro ((III)) con un ligando derivado de 2- ((2-piridil) etilamina (L ((Py1Bz)).
Estudios cinéticos detallados para determinar las constantes de velocidad de reacción (k(1) y k(2)).
Análisis del efecto del potencial de oxidación del sustrato en la velocidad de reacción.

Principales resultados:

El complejo bis (mu-oxo) dicopro (III) catalizó con éxito la oxigenación de sulfuros a sulfóxidos.
El análisis cinético reveló un mecanismo de dos pasos: asociación de sustrato seguido de transferencia de átomos de oxígeno intramolecular.
El paso que determina la velocidad (k(2) fue insensible al potencial de oxidación del sustrato, lo que indica un mecanismo directo de transferencia de átomos de oxígeno.

Conclusiones:

Un nuevo complejo bis ((mu-oxo) dicopro ((III) es un catalizador eficaz para la oxigenación del sulfuro.
La reacción se produce a través de un mecanismo directo de transferencia de átomos de oxígeno, que no implica la transferencia de electrones.
Este trabajo proporciona nuevos conocimientos sobre la catálisis de oxidación mediada por cobre.

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