Тиобензолсульфонат тетрафенилфосфора. Синтез и строение

Abstract

The reaction of pentaphenylphosphorus with sulfur dioxide SO2 (glass ampoule, 24 C, 1 h) followed by recrystallization of the target product from water has given tetraphenylphosphonium thiobenzenesulfonate [Ph4P]+ [PhSO2S] (1). Complex 1 has been characterized by X-ray structural analysis and IR spectroscopy. It has the form of colorless crystals with m.p. 164 °C, soluble in arenes and polar solvents. The IR spectrum of complex 1 contains bands characterizing the vibrations of the PC bonds (756 cm1), SS (488 cm1), SO2 (1109, 1234 cm1), and phenyl groups (3055, 1439, 1020, 691 cm1). The X-ray structural analysis of the complex has been carried out on an automatic four-circle D8 Quest Bruker diffractometer (MoKα radiation, λ = 0.71073 Å, graphite monochromator) at 293 K. Crystallographic characteristics: 1  monoclinic syngony, space group P21/n, a = 10.419(17), b = 13.23(2), c = 18.58(4) Å, β = 99.74(5) degrees, V = 2524(8) Å3, Z = 4, calc = 1.349 g/cm3, F(000) = 1073.8, crystal size 0.14  0.14  0.1 mm, reflection index intervals 18 ≤ h ≤ 18, 21 ≤ k ≤ 21, 22 ≤ l ≤ 22, total reflections 96987, inde-pendent reflections 16158 (Rint = 0.0701), number of refined parameters 392, GOOF 1.060, R-factors for F2>2σ(F2): R1 = 0.1304, wR2 = 0.2093. Crystal 1 consists of tetrahedral tetraphenylphosphonium cations and thiobenzenesulfonate anions, in which the negative charge is localized on the terminal sulfur atom (SS 1.940(3) Å, S = O 1.443(5), 1.449(4) Å, SC 1.775(6 ) Å).