Strikingly diverse reactivity of structurally identical silylene and stannylene.

The reactivity of structurally identical silylene and stannylene [PhC(NtBu)EN(SiMe)] (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)SnX (X = Br (6), Cl (7), and OSOCF (8)) with concomitant formation of [M{N(SiMe)}] (M = Cu, Ag). However, with AgSbF both 1 and 2 led to ion pairs, 9·SbFand 10·SbF displaying weaker Ag·F interactions in the latter.