The ditriflate salt of the DMAP-stabilized trimethylphosphane dication is formed from the reaction of chlorotrimethylphosphonium triflate with DMAP (4-dimethylaminopyridine) in the presence of trimethylsilyltriflate and also from the reaction of DMAP-dimethylphosphenium triflate with methyltriflate. The coordinative nature of the DMAP–phosphorus bond is demonstrated by a ligand exchange of DMAP for PMe3 to give the hexamethyldiphosphonium dication. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)