Utility of Three-Coordinate Silver Complexes Toward the Formation of Iodonium Ions.

The work herein describes the synthesis of five three-coordinate silver(I) complexes comprising a bidentate ligand L1, either bpy (2,2'-bipyridyl) or bpyMe (4,4'-dimethyl-2,2'-dipyridyl), and a monodentate ligand L2, either mtz (1-methyl-1H-1,2,3-triazole), 4-Etpy (4-ethylpyridine), or 4-DMAP (,-dimethylpyridin-4-amine). Upon reaction of the three-coordinate silver(I) complexes with 0.5 equiv of I, the reactions quantitatively produce a 1:1 pair of complexes of a four-coordinate silver(I) complex [Ag(L1)]PF and a two-coordinate iodonium complex [I(L2)]PF. The combination of [Ag(bpyMe)]PF and [I(4-DMAP)]PF gave rise to an I···Ag interaction where the I acts as a nucleophile, only the second example of which, that was observed in both the solution (NMR) and solid (X-ray) states.