Oligomethylene-bridged dinuclear triorganotin triflates and diphenylphosphinates. Ion pairing in the solid state and electrolytic dissociation in solution of [Ph2Sn(CH2)nSnPh2X](O3SCF3) (X = OH, O2PPh2; n = 1-3)

The condensation of [Ph2(OH)Sn(CH2)nSn(OH)Ph2] (1-3; n = 1-3) with HO3SCF3 and HO2PPh2 provided [Ph2Sn(CH2)nSnPh2(OH)](O3SCF3) (4-6; n = 1-3) and [Ph2(O2PPh2)Sn(CH2)nSn(O2PPh2)Ph2] (10-12; n = 1-3), respectively. The reaction of [Ph2Sn(CH2)nSnPh2(OH)](O3SCF3) (4-6; n = 1-3) with HO2PPh2 and NaO2PPh2 gave rise to the formation of [Ph2Sn(CH2)nSnPh2(O2PPh2)](O3SCF3) (7-9; n = 1-3) and [Ph2(OH)Sn(CH2)nSn(O2PPh2)Ph2] (13-15; n = 1-3), respectively. In the solid state, compounds 4-9 comprise ion pairs of cationic cyclo-[Ph2SnCH2SnPh2(OH)]22+, cyclo-[Ph2Sn(CH2)nSnPh2(OH)]+ (n = 2, 3), and cyclo-[Ph2Sn(CH2)nSnPh2(O2PPh2)]+ (n = 1-3) and triflate anions. In MeCN, the eight-membered-ring system cyclo-[Ph2SnCH2SnPh2(OH)]22+ appears to be in equilibrium with the four-membered-ring system cyclo-[Ph2SnCH2SnPh2(OH)]+. In contrast, compounds 10-15 show no ionic character. Compounds 1-15 were characterized by multinuclear NMR spectroscopy in solution and in the solid state, IR spectroscopy, conductivity measurements, electrospray mass spectrometry, osmometric molecular weight determinations, and X-ray crystallography (4, 5, 7, and 12).