The crystal structures of bis-pyridine stabilized iodine dications [PhI(pyr)(2)](2+) are reported as triflate salts, representing the first ligand supported iodine dications to be structurally characterized. The pyridine complexes are susceptible to ligand exchange in reaction with stronger N-based donors such as 4-dimethylaminopyridine. Attempts to extend this reactivity to N-heterocyclic carbene and phosphine ligands, as has been accomplished in the earlier p-block groups, resulted in redox chemistry, with oxidation of the ligands rather than coordination.