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A CuI /CuIII prototypical organometallic mechanism for the deactivation of an active pincer-like CuI catalyst in Ullmann-type couplings

Unraveling the mechanistic details of copper-catalyzed arylation of nucleophiles (Ullmann-type couplings) is a very challenging task. It is a matter of intense debate whether it is a radical-based process or an organometallic redox- based process. The ancillary ligand choice in Ullmann-type couplings plays a key role in such transformations and can strongly influence the catalytic efficiency as well as the mechanism. Here, we show how a predesigned tridentate pincer-like catalyst undergoes a deactivation pathway through a Cu I /Cu III prototypical mechanism as demonstrated by helium-tagging infrared photodissociation (IRPD) spectroscopy and DFT studies, lending a strong support to the existence of an aryl-Cu III species in the Ullmann couplings using this tridentate ligand

Royal Society of Chemistry (RSC)

Author: Rovira Coll, Mireia
Jašíková, Lucie
Andris, Erik
Acuña-Parés, Ferran
Soler Vives, Marta
Güell Costa, Imma
Wang, Ming Zheng
Gómez Martín, Laura
Luis Luis, Josep Maria
Roithová, Jana
Ribas Salamaña, Xavi
Date: 2018 June 5
Abstract: Unraveling the mechanistic details of copper-catalyzed arylation of nucleophiles (Ullmann-type couplings) is a very challenging task. It is a matter of intense debate whether it is a radical-based process or an organometallic redox- based process. The ancillary ligand choice in Ullmann-type couplings plays a key role in such transformations and can strongly influence the catalytic efficiency as well as the mechanism. Here, we show how a predesigned tridentate pincer-like catalyst undergoes a deactivation pathway through a Cu I /Cu III prototypical mechanism as demonstrated by helium-tagging infrared photodissociation (IRPD) spectroscopy and DFT studies, lending a strong support to the existence of an aryl-Cu III species in the Ullmann couplings using this tridentate ligand
Document access: http://hdl.handle.net/2072/319858
Language: eng
Publisher: Royal Society of Chemistry (RSC)
Rights: Attribution-NonCommercial 3.0 Spain
Rights URI: http://creativecommons.org/licenses/by-nc/3.0/es/
Subject: Catalitzadors de coure
Copper catalysts
Catàlisi
Catalysis
Reaccions químiques
Chemical reactions
Title: A CuI /CuIII prototypical organometallic mechanism for the deactivation of an active pincer-like CuI catalyst in Ullmann-type couplings
Type: info:eu-repo/semantics/article
Repository: Recercat

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