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Estructuralmente Caracterizado por el par μ-1,2-Peroxo/Superoxo Dicopio
Alexander Brinkmeier1, Roland A Schulz1, Moritz Buchhorn2
1Institut für Anorganische Chemie, Universität Göttingen, Tammannstraße 4, D-37077 Göttingen, Germany.
Journal of the American Chemical Society
|June 30, 2021
Resumen
Este estudio informa de la primera estructura cristalográfica de un complejo de superóxido de cobre, un intermediario clave en la química del cobre y el oxígeno. Esta visión estructural explica la fácil interconversión entre las especies de superoxo y peroxo dicopper.
Área de la Ciencia:
- Química bioorgánica
- Química de coordinación
- Catalización por oxidación
Sus antecedentes:
- Los complejos superóxido de cobre son cruciales en las reacciones de oxidación y las metalloenzimas activadoras de oxígeno.
- Su alta reactividad hace que el aislamiento y la caracterización estructural sean desafiantes.
- Los trabajos anteriores establecieron datos termoquímicos, pero carecían de detalles estructurales de las especies de superóxido de cobre.
Objetivo del estudio:
- Informar de la primera estructura cristalográfica de una especie de superoxo dicopero.
- Para caracterizar su congénero peroxo y su interconversión.
- Proporcionar información estructural sobre la reactividad de estos intermediarios clave de cobre y oxígeno.
Principales métodos:
- Determinación de la estructura cristalográfica de los complejos de superóxido y peroxo dicobre.
- Estudios electroquímicos para determinar los potenciales redox y la reversibilidad.
- Análisis espectroscópico (IR, EPR) y mediciones magnéticas.
- Cálculos de la teoría funcional de la densidad (DFT).
Principales resultados:
- Determinación de la primera estructura cristalográfica de una especie de dicobre superoxo (II) (3) y de su congénere peroxo (2).
- Reversible 1e- Interconversión entre los complejos 2 y 3 a bajo potencial (-0,58 V vs Fc/Fc+).
- Los datos estructurales y espectroscópicos confirman la actividad redox en la unidad derivada de O2.
- El complejo CuII-superoxo-CuII exhibe un estado básico de espín de S = 1/2.
- Los cálculos de DFT revelan superficies de energía potencial poco profundas para los cambios de ángulo diédrico.
Conclusiones:
- El estudio proporciona la primera caracterización estructural de un complejo superoxo dicopro (II).
- Los hallazgos estructurales y computacionales explican la fácil interconversión de energía de baja reorganización de las parejas μ-1,2-superoxo/peroxo dicopro (II).
- Estos resultados ofrecen una base para investigaciones adicionales sobre la química del cobre y el oxígeno y los mecanismos enzimáticos relacionados.
![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
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