The work herein describes the synthesis of five three-coordinate silver(I) complexes comprising a bidentate ligand L1, either bpy (2,2′-bipyridyl) or bpyMe2 (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 (N,N-dimethylpyridin-4-amine). Upon reaction of the three-coordinate silver(I) complexes with 0.5 equiv of I2, the reactions quantitatively produce a 1:1 pair of complexes of a four-coordinate silver(I) complex [Ag(L1)2]PF6 and a two-coordinate iodonium complex [I(L2)2]PF6. The combination of [Ag(bpyMe2)2]PF6 and [I(4-DMAP)2]PF6 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.