Beschreibung:
<jats:title>Abstract</jats:title><jats:p>Despite the known nucleophilic nature of [M(CF<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>]<jats:sup>−</jats:sup> (M=Cu, Ag, Au) complexes, their participation in trifluoromethylation reactions of aryl halides remains unexplored. Here, for the first time, selective access to a [Cu(CF<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>]<jats:sup>−</jats:sup> species is reported, which is ubiquitous in Cu‐mediated trifluoromethylations, and we rationalize its complex mechanistic scenario as well as its behavior compared to its silver and gold congeners through a combination of experimental and computational approaches.</jats:p>