Beyond the traditional roles of Ag in catalysis: the transmetalating ability of organosilver(i) species in Pd-catalysed reactions.

Silver salts are one of the most widely used additives in Pd-catalysed transformations. Apart from acting as a halide scavenger and/or an external oxidant, over the past decade it has been revealed that silver salts can play other roles such as a C-H activation promoter or decarboxylating agent, generating organosilver(i) species. These nucleophiles can promote innovative transformations by reacting with PdII intermediates through a transmetalation step. This review article covers different Pd-catalysed C-C bond-forming reactions where silver complexes have been proposed to act as nucleophilic coupling partners. We will also provide relevant mechanistic features associated with these transformations.