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Cobre ((I) Acoplamiento Reductivo de Óxido Nítrico Mediado Complejo: Enlace de Hidrógeno Ligando Transferencia de

Gayan B Wijeratne¹, Mayukh Bhadra¹, Maxime A Siegler¹

¹Department of Chemistry , The Johns Hopkins University , Baltimore , Maryland 21218 , United States.

Journal of the American Chemical Society

|October 18, 2019

Resumen

Un nuevo complejo de cobre convierte eficientemente el gas de óxido nítrico en gas de óxido nitroso. Este proceso se basa en el enlace de hidrógeno y la acidez dentro del complejo para una escisión efectiva del enlace N-O.

Área de la Ciencia:

Química inorgánica
Catálisis
Sistemas bioquímicos

Sus antecedentes:

El óxido nítrico (NO) es una molécula de señalización crítica en los sistemas biológicos.
La conversión eficiente de NO es importante tanto para aplicaciones químicas como biológicas.
Los complejos de cobre son catalizadores conocidos para varias transformaciones químicas.

Objetivo del estudio:

Desarrollar un sistema catalítico para la conversión eficiente del óxido nítrico (NOg) en óxido nitroso (N2Og).
Investigar el papel de los enlaces de hidrógeno y la acidez en el mecanismo catalítico.
Para comprender la escisión del enlace N-O en las reacciones de acoplamiento NO.

Principales métodos:

Síntesis de un complejo de quelato de cobre, [(PV-tmpa) CuI]+, con enlace de hidrógeno de esfera secundaria.
Reacción del complejo de cobre con el NOg en el metanol.
Análisis de los productos de reacción e intermedios para determinar el rendimiento y el mecanismo.

Principales resultados:

El complejo [(PV-tmpa) CuI]+ demostró altos rendimientos en la conversión de NOg en N2Og en el metanol.
La transferencia de protones derivada del ligando fue identificada como un paso clave en la escisión del enlace N-O.
Se propuso un intermediario hipotético de hiponitrito en la vía de reacción.

Conclusiones:

El estudio destaca un nuevo catalizador a base de cobre para la transformación de NOg.
Los hallazgos subrayan la importancia de equilibrar el enlace de hidrógeno y la acidez en las reacciones de acoplamiento de NO.
Este trabajo proporciona información sobre los sistemas catalíticos para las transformaciones (bio) químicas de NO.

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