Organometallic coinage metal complexes have proven to be key reactive species for promoting a wide variety of chemical transformations. Our main interest lies in understanding the behavior of these complexes in relevant CC and/or CN bond-forming reactions. In this context, we have explored: i) the mechanistic intricacies of copper species as co-catalyst in the context of rhodium/copper-catalyzed oxidative coupling reactions; ii) the capability of silver nucleophiles as transmetalating agents in palladium-catalyzed trifluoromethylation reactions; iii) the mechanistic landscape of the transmetalation step in palladium/silver bimetallic reactions using a model system; and iv) the role of bis-(trifluoromethyl) coinage metallates as nucleophiles, focusing our attention on the trifluoromethylation of aryl halides. The fundamental insights gathered during this research, encompassing both experimental and computational approaches, are essential in the context of knowledge-driven research in Chemistry.