2,3-Diphosphino-1,4-diphosphonium ions

Salts of the first crystallographically characterized chlorophosphinophosphonium ions have been prepared, and their reaction with Ph3P results in reductive coupling of the chlorophosphine centers to give the first acyclic 2,3-diphosphino-1,4-diphosphonium ions, representing a key framework in the development of catena-phosphorus chemistry. These new salts of general formula R3P-PR'-PR'-PR3]OTf]2 are also obtained in a one-pot diastereoselective reaction of a dichlorophosphine, a tertiary phosphine, and trimethylsilyltrifluoromethanesulfonate. The structural and spectroscopic features of the new dications complement those of the known diphosphonium and 2-phosphino-1,3-diphosphonium dications. Quantitative ligand exchange reactions are observed when derivatives of Ph3P-PR'-PR'-PPh3]OTf]2 are combined with Me3P, demonstrating the coordinative nature of the phosphine-phosphonium P-P bonds and implicating a bonding model involving the diphosphenium dication acceptor. The observed solid state structures have been interpreted in the context of computational studies.