Based on the analysis of literature sources from the beginning of the 21st century to the present, various methods for obtaining phosphorus compounds of the general formula R4PX (X is an electronegative group) have been systematized and described. The present study is a continuation of classical research in the field of chemistry of organic phosphorus compounds in the Laboratory of Chemistry of Organoelement Compounds of South Ural State University. The prin-cipal attention is paid to synthesis methods for tetraorganylphosphonium derivatives based on radical redistribution reactions and substitution reactions, which are used to synthesize tetra-phenylphosphorus bromide and a series of alkyltriphenylphosphonium arenesulfonates, respec-tively. It has been shown that the single product of the interaction of triphenylphosphorus dibro-mide with pentaphenylphosphorus in a benzene solution (1 hour, 25 °C) is tetraphenylphosphoni-um bromide, isolated from the reaction mixture, yielding 92%. Tetraphenylphosphonium benzene-sulfonate has been obtained, yielding 90%, by a substitution reaction from tetraphenylphosphoni-um bromide and benzenesulfonic acid in water. Using a similar scheme, a series of alkyltri-phenylphosphonium arenesulfonates have been obtained with yields up to 92 %: [Ph3PC3H5-cyclo][OSO2Naft-1] (2), [Ph3PCH2СN][OSO2Mez)] (3), [Ph3PCH2СN][OSO2C6H3Сl2-2,5] ∙ ½MeOH (4), [Ph3PCH2OH][OSO2C6H3Сl2-2,5] ∙ H2O (5), [Ph3PEt][OSO2C6H3(NO2)2-2,4] (6), [Ph3P(СH2)2OH] [OSO2C6H3(NO2)2-2,4] (7), [Ph3P(С6H11-cyclo)] [OSO2C6H3(NO2)2-2,4] (8). The complex structures have been proved by IR spectroscopy and X-ray diffraction analysis (XRD). According to the XRD data, crystals of complexes 2–5 have ionic structure; they consist of tetraorganylphosphonium and arenesulfonate anions.
Tris(2-methoxyphenyl)antimony bis[3,4-difluorobenzoate] (1) and tris(2-methoxyphenyl)antimony bis[benzenesulfonate] (2) were obtained by oxidative addition reaction from triarylantimony and 3,4-difluorobenzoic/benzenesulfonic acid in the presence of tertiary bu-tyl hydroperoxide in ether. The structure of 1 and 2 was established with the use of IR spectrosco-py and X-ray diffraction analysis (XRD). Crystals 1 [C35H27O7F4Sb, M 757.32; triclinic syngony, symmetry group P–1; cell parameters: a = 9.219(4), b = 9.507(6), c = 20.240(11) Å; a = 99.43(3)°, β = 95.756(16)°, g = 107.90(3)°; V = 1643.6(16) Å3; Z = 2; rcalc = 1.530 g/cm3; 2q 6.68-54.98 de-grees; total reflections 31858; independent reflections 7153; number of specified parameters 427; Rint = 0.0429; GOOF 1.051; R1 = 0.0265, wR2 = 0.0551; residual electron density (max/min); 0.30/-0.44 e/Å3], 2 [C33H31O9S2Sb, M 757.46; monoclinic system, symmetry group C2/c; cell parame-ters: a = 21.157(9), b = 10.363(4), c = 18.285(7) Å; β = 126.590(13) deg., V = 3219(2) Å3, Z = 1; rcalk = 1.563 g/cm3; 2q 6.012-54.234 degrees; total reflections 32454; independent reflections 3541; number of specified parameters 231; Rint = 0.0283; GOOF 1.161; R1 = 0.0283, wR2 = 0.0659; residual electron density (max/min); 0.74/-0.83 e/Å3] consist of trigonal bipyramidal molecules with electronegative ligands in axial positions. The Sb–C bond lengths vary in the range 2.093(2)−2.125(3) Å, The OSbO bond angles take values 176.63(6)° and 174.52(10)°, respective-ly. The Sb–O distances in 1 (2.1106(17) and 2.1149(17) Å) are shorter than in 2 (2.128(2) and 2.128(2) Å). Intramolecular Sb∙∙∙O contacts in 1 (3.162(2) and 3.257(2) Å) are significantly smaller than in 2 (3.617(2) and 3.617(2) Å) and do not exceed the sum of their van der Waals radii (3.7 Å). Complete tables of atomic coordinates, bond lengths and bond angles for structures have been de-posited in the Cambridge Structural Data Bank (No. 2123247 (1), No. 2116583 (2), depos-it@ccdc.cam.ac.uk; http://www.ccdc cam.ac.uk).
The reaction of equimolar amounts of alkyltriphenylphosphonium bromides with organosulfonic acids in water yielded ionic alkyltriphenylphosphonium organosulfonates [Ph3PC6H11-cyclo][OSO2CF3] (1), [Ph3PCH2CN][OSO2CF3] (2), [Ph3PC6H11-cyclo][OSO2C6H3(NO2)2-2,4] (3), [Ph3PCH2С6H4(OH-2)][OSO2C6H3Me2-2,5] (4), [Ph3P(CH2)4Br][OSO2C6H3Me2-2,5] (5). The struc-ture of complexes 1–5 was determined by elemental analysis and IR spectroscopy.
