Reactions of Butenbis(triphenylphosphonium) and Pentanebis(triphenylphosphonium) Bromides with Arenesulfonic Acids

By the reaction of equimolar amounts of tetraorganylphosphonium bromides with arenesulfonic acids in water, ionic tetraorganylphosphonium arenesulfonates Ph3PCH2CH=CHCH2PPh3OSO2C9H3N(OH-4)(I-7)2 ∙ 4H2O (1), Ph3P(CH2)5PPh3 OSO2С6H4(COOH-2)Br (2) were obtained with a yield of up to 89%. The structural features of complexes 1 and 2 were established by X-ray diffraction. Crystals: 1 C58H54I2N2O12P2S2, M 1350.89; triclinic system, symmetry group P-1; cell parameters: a = 9.506(8) Å, b = 11.323(12) Å, c = 13.662(10) Å; α = 82.21(4)°, β = 89.26(2)°, γ = 72.60(4)°, V = 1390(2) Å3, Z = 2; ρcalcd = 1.614 g/cm3; 2 C48H45O5P2SBr, M 875.75; triclinic system, symmetry group P-1; cell parameters: a = 10.307(7) Å, b = 14.226(9) Å, c = 16.291(10) Å; α = 67.07(3)°, β = 83.74(3)°, γ = 74.65(3)°, V = 2122(2) Å3, Z = 2; ρcalcd = 1.371 g/cm3 consist of tetraorganylphosphonium cations and arene-sulfonate anions with a tetrahedral sulfur atom. The crystal of complex 2 also contains Br− anions. The P–C bond lengths vary in the range 1.779(3)−1.815(4) Å. The bond angles of the CPC take values of 104.33(15)°−112.00(10)°. The S–O distances vary within the range of 1.4397(18)−1.4576(19) Å. Complete tables of atomic coordinates, bond lengths and bond angles for structures have been deposited in the Cambridge Structural Data Bank (CCDC nos. 2164291 (1) and 2165072 (2)).