The interaction of a [bis(pyridine)iodine(I)]+ cation with a [bis(pyridine)silver(I)]+ cation, in which an iodonium ion acts as a nucleophile by transferring electron density to the silver(I) cation, is reinvestigated herein. No measurable interaction is observed between the cationic species in solution by NMR; DFT reveals that if there is an attractive interaction between these complexes in solution, it is dominantly the π-π interaction of pyridines.