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Estructura electrónica del catalizador [Fe(salen)]2-μ-oxo y su efecto en la hidroaminación reductiva

Emily Pocock¹, Nathan J Buxton², Martin Diefenbach³

¹Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.

Inorganic chemistry

|December 20, 2025

Resumen

Los complejos de hierro-salen catalizan la hidroaminación reductiva de nitroarenos. La electrónica del ligando ajusta la eficiencia, y los complejos de hierro-salen sustituidos con para-CF3 muestran un rendimiento superior en la catálisis de transferencia de hidrógeno atómico.

Área de la Ciencia:

Química Organometálica
Catálisis
Síntesis Orgánica

Sus antecedentes:

Los ligandos Salen son versátiles en la catálisis de metales de transición, ofreciendo electrónica sintonizable y estabilidad redox.
Los complejos de hierro-salen se exploran cada vez más para aplicaciones catalíticas debido a la abundancia y baja toxicidad del hierro.

Objetivo del estudio:

Sintetizar y comparar tres complejos [Fe(salen)]2(μ-oxo) electrónicamente diferenciados.
Investigar su eficacia en la hidroaminación (HA) reductiva catalítica de nitroarenos con alquenos.
Elucidar el mecanismo, centrándose en el papel de la electrónica del ligando en la transferencia de hidrógeno atómico (HAT).

Principales métodos:

Síntesis de complejos de hierro-salen electrónicamente variados.
Pruebas catalíticas en reacciones de hidroaminación reductiva.
Estudios mecanísticos que incluyen espectroscopía UV-vis, voltametría cíclica, cálculos DFT y análisis de la energía LUMO del sustrato.

Principales resultados:

Síntesis exitosa de tres complejos [Fe(salen)]2(μ-oxo) con distintas propiedades electrónicas.
Demostración de actividad catalítica en la HA de nitroarenos.
Identificación de intermedios de hierro-hidruro y un mecanismo de transferencia de hidrógeno atómico (HAT).
El complejo con sustituyentes para-CF3 exhibió una eficiencia catalítica mejorada y un alcance de sustrato más amplio.

Conclusiones:

La electrónica del ligando influye críticamente en el rendimiento de los catalizadores de hierro-salen en reacciones basadas en HAT.
El complejo sustituido con para-CF3 representa un pre-catalizador altamente efectivo para la hidroaminación reductiva.
Este trabajo proporciona un marco para el diseño de catalizadores avanzados de hierro-salen mediante la sintonización de la electrónica del ligando.

Palabras clave:

hidroaminación reductiva complejos de hierro-salen catálisis transferencia de hidrógeno atómico electrónica del ligando

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