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)<i>_n</i>Sn(OH)Ph₂] (<b>1-3</b>; <i>n</i> = 1-3) with HO₃SCF₃ and HO₂PPh₂ provided [Ph₂Sn(CH₂)_<i>n</i>SnPh₂(OH)](O₃SCF₃) (<b>4-6</b>; <i>n</i> = 1-3) and [Ph₂(O₂PPh₂)Sn(CH₂)_<i>n</i>Sn(O₂PPh₂)Ph₂] (<b>10-12</b>; <i>n</i> = 1-3), respectively. The reaction of [Ph₂Sn(CH₂)_<i>n</i>SnPh₂(OH)](O₃SCF₃) (<b>4-6</b>; <i>n</i> = 1-3) with HO₂PPh₂ and NaO₂PPh₂ gave rise to the formation of [Ph₂Sn(CH₂)_<i>n</i>SnPh₂(O₂PPh₂)](O₃SCF₃) (<b>7-9</b>; <i>n</i> = 1-3) and [Ph₂(OH)Sn(CH₂)_<i>n</i>Sn(O₂PPh₂)Ph₂] (<b>13-15</b>; _<i>n</i> = 1-3), respectively. In the solid state, compounds <b>4-9</b> comprise ion pairs of cationic cyclo-[Ph₂SnCH₂SnPh₂(OH)]₂²⁺, cyclo-[Ph₂Sn(CH₂)<i>_n</i>SnPh₂(OH)]⁺ (<i>n</i> = 2, 3), and cyclo-[Ph₂Sn(CH₂)_<i>n</i>SnPh₂(O₂PPh₂)]⁺ (<i>n</i> = 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 <b>10-15</b> show no ionic character. Compounds <b>1-15</b> 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 (<b>4, 5, 7,</b> and <b>12</b>). <br><br>