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Comportamiento similar al de los metales de transición de los elementos del grupo principal: intercambio de ligandos

Max M Hansmann¹, Guy Bertrand¹

¹UCSD-CNRS Joint Research Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California, San Diego , La Jolla, California 92093-0358, United States.

Journal of the American Chemical Society

|December 15, 2016

Resumen

Los fosfacetenos (fosfino) funcionan como añadidos de fosfinideno-carbonilo. Las reacciones de intercambio de ligandos con CO, fosfinas, isonitriles y carbenos ocurren a través de un mecanismo asociativo, similar a los complejos de metales de transición.

Área de la Ciencia:

Química de los organofosforados
Mecanismos de reacción inorgánicos

Sus antecedentes:

Los (fosfato) fosfaténicos son una clase única de compuestos de fósforo.
Su reactividad y características de enlace no se comprenden completamente.

Objetivo del estudio:

Para aclarar el enlace y la reactividad de los (fosfino) fosfatenos.
Investigar el mecanismo de las reacciones de intercambio de ligandos que involucran a estos compuestos.

Principales métodos:

Síntesis y caracterización de los (fosfino) fosfaténicos.
Estudios de etiquetado isotópico con CO marcado con 13C.
Las reacciones de intercambio de ligandos con varios sustratos (fosfinas, isonitrilos, carbenos).
Cálculos de la Teoría Funcional de la Densidad (DFT).

Principales resultados:

Se ha demostrado que los (fosfácetenos) actúan como aductos de (fosfino) fosfinideno carbonilo.
Se observaron reacciones de mezcla y intercambio de CO con fosfinas, isonitriles y carbenos.
Los cálculos DFT apoyaron los hallazgos experimentales.

Conclusiones:

Las reacciones de intercambio de ligandos de los (fosfino) fosfacetenos proceden a través de un mecanismo asociativo.
Este mecanismo es análogo a los observados en los complejos de metales de transición, destacando un tema mecanicista común en diversos sistemas químicos.

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