The reactivity of structurally identical silylene and stannylene [PhC(NtBu)2EN(SiMe3)2] (E = Si (1) and Sn (2)) towards coinage metals has been explored. While 1 has the propensity to form an adduct with coinage metals (4 and 5), 2 undergoes a ligand exchange reaction with copper halides and silver triflate leading to PhC(NtBu)2SnX (X = Br (6), Cl (7), and OSO2CF3 (8)) with concomitant formation of [M{N(SiMe3)2}] (M = Cu, Ag). However, with AgSbF6 both 1 and 2 led to ion pairs, 9+·SbF6-and 10+·SbF6- displaying weaker Ag·F interactions in the latter.