A CuI/CuIII prototypical organometallic mechanism for the deactivation of an active pincer-like CuI catalyst in
Mireia Rovira1, Lucie Jašíková2, Erik Andris2
1Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus de Montilivi, E-17003 Girona, Catalonia, Spain. xavi.ribas@udg.edu.
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 CuI/CuIII prototypical mechanism as demonstrated by helium-tagging infrared photodissociation (IRPD) spectroscopy and DFT studies, lending a strong support to the existence of an aryl-CuIII species in the Ullmann couplings using this tridentate ligand.
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