Sharutin V.V. Tetraphenylphosphonium Thiobenzenesulfonate. Synthesis and Structure

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) ų, Z = 4, r_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, independent reflections 16158 (R_int = 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).