A Cu-I/Cu-III prototypical organometallic mechanism for the deactivation of an active pincer-like Cu-I catalyst in Ullmann-type couplings
Abstrakt
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.