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Transferencia intramolecular de un solo electrón entre ligando redox-activo intramolecular y sustrato: reactividad

Daniël L J Broere¹, Bas de Bruin, Joost N H Reek

¹Homogeneous, Bioinspired & Supramolecular Catalysis, van 't Hoff Institute for Molecular Sciences, University of Amsterdam , Science Park 904, 1098 XH Amsterdam, The Netherlands.

Journal of the American Chemical Society

|June 14, 2014

Resumen

Este estudio detalla un complejo de paladio con un ligando redox-activo que facilita la aminación C-H. El ligando es el ligando.

Área de la Ciencia:

Química organometálica Química orgánica de los metales.
La catálisis de la catálisis.
Los ligandos redox-activos de las ligandas.

Sus antecedentes:

Los complejos de paladio son cruciales en la catálisis.
Los ligandos redox-activos ofrecen propiedades electrónicas únicas.
La comprensión de los mecanismos de reacción es clave para el diseño de catalizadores.

Objetivo del estudio:

Para sintetizar y caracterizar un nuevo complejo de paladio (II) con un ligando NNO redox-activo.
Para investigar el mecanismo de activación de azido alifático y C-H aminación.
Explorar el papel del ligando redox-activo en el ciclo catalítico.

Principales métodos:

Síntesis del complejo iminobenzosemiquinonato de paladio (II).
Reducción de un solo electrón al complejo amidofenolato.
Estudios experimentales y modelado computacional de la vía de reacción.

Principales resultados:

Formación de un complejo iminobenzosemiquinonato paramagnético (3) y su derivado diamagnético amidofenolato (4).
El complejo 4 activa la azida alifática (5).
Se propuso un mecanismo redox-noninnocente que involucra la transferencia de electrones intramolecular de ligando a sustrato, generando un radical nitreno-sustrato y un radical ligando.

Conclusiones:

El ligando redox-activo juega un papel crítico en la facilitación de la aminación C-H a través de una vía radical.
Este trabajo proporciona información sobre el mecanismo de las reacciones de aminación catalizadas por el paladio.
Los hallazgos contribuyen al desarrollo de nuevos sistemas catalíticos que utilizan ligandos redox-activos.

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