Exploring the Role of Coinage Metalates in Trifluoromethylation: A Combined Experimental and Theoretical Study.

Despite the known nucleophilic nature of [M(CF3 )2 ]- (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(CF3 )2 ]- 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.