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Coordinación de alcano por un complejo de magnesio ácido neutro de Lewis

Jeremy C Mullins¹, Matthew J Evans¹, Joseph M Parr¹

¹School of Chemistry, Monash University, P.O. Box 23, Melbourne, Victoria 3800, Australia.

Journal of the American Chemical Society

|December 8, 2025

Resumen

Este resumen es generado por máquina.

Este estudio sintetiza nuevos complejos de diamida de magnesio que forman los primeros complejos de metal-alcano/TMS del grupo 2. Estos complejos exhiben un enlace débil pero significativo, con interacciones electrostáticas dominantes.

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Área de la Ciencia:

Química organometálica
Química del grupo principal
Química de coordinación

Sus antecedentes:

Se sintetizaron las diamidas de magnesio ácido de Lewis con geometrías restringidas.
La cristalografía de rayos X reveló estructuras diméricas con coordinación intermolecular.

Objetivo del estudio:

Síntesis y caracterización de los primeros complejos metal-alcano/TMS del grupo 2.
Para investigar las interacciones de unión dentro de estos nuevos complejos.

Principales métodos:

Síntesis de complejos de diamida de magnesio.
Difracción de rayos X y neutrones para la determinación estructural.
Cálculos de la teoría funcional de la densidad (DFT), incluidos los análisis ETS-NOCV y NBO.
Interacción no covalente (NCI) y análisis de la teoría cuántica de los átomos en las moléculas (QTAIM).

Principales resultados:

Se sintetizaron tres nuevos complejos de diamida de magnesio (1-3).
Los complejos 1 y 2 adoptaron estructuras diméricas.
Los primeros complejos metal-alcano/TMS del grupo 2 (4-6) se formaron mediante el tratamiento del complejo 1 con n-pentano, n-hexano o tetrametilsilano (TMS).
El análisis estructural confirmó las formulaciones de los complejos 4-6.
Los cálculos de DFT indicaron un enlace débil entre el alcano/TMS y el fragmento de magnesio, comparable a los complejos de metales de transición.
Se encontró que las interacciones electrostáticas eran el componente de enlace dominante (aprox. 65%), con contribuciones significativas de la dispersión (aprox. 20%) y las interacciones orbitales (aprox. El 15%).

Conclusiones:

El estudio informa de los primeros ejemplos de complejos metal-alcano/TMS del grupo 2.
La unión en estos complejos se caracteriza por una combinación de interacciones electrostáticas, de dispersión y orbitales.
El bolsillo de coordinación lipofílico influye en las fuerzas de dispersión, y el flujo de carga del alcano / TMS al magnesio contribuye a las interacciones orbitales.