Тиобензолсульфонат тетрафенилфосфора. Синтез и строение

Владимир Викторович Шарутин

Аннотация


Взаимодействием пентафенилфосфора с оксидом серы SO2 (стеклянная ампула, 24 °С, 1 ч) cпоследующей перекристаллизацией целевого продукта из воды получен тиобензолсульфонат тетрафенилфосфония [Ph4P]+ [PhSO2S]- (1). Комплекс 1 охарактеризован методами рентгеноструктурного анализа и ИК-спектроскопии. Представляет собой бесцветные кристаллы с т. пл. 164 °С, растворимые в аренах и полярных растворителях. В ИК-спектре комплекса 1 присутствуют полосы, характеризующие колебания связей P-C (756 см-1), S-S (488 см-1), SO2 (1109, 1234 см-1) и фенильных групп (3055, 1439, 1020, 691 см-1). Рентгеноструктурный анализ комплекса проводили на автоматическом четырехкружном дифрактометре D8 Quest Bruker (Мо Kα-излучение, λ = 0,71073 Å, графитовый монохроматор) при 293 К. Кристаллографические характеристики: 1 - моноклинная сингония, пространственная группа P21/n, a= 10,419(17), b = 13,23(2), c = 18,58(4) Å, β = 99,74(5) град., V = 2524(8) Å3, Z = 4, rвыч = 1,349  г/см3, F(000) = 1073,8, размер кристалла 0,14 ´ 0,14 ´ 0,1 мм, интервалы индексов отражений 18 ≤ h ≤ 18, -21 ≤ k ≤ 21, -22 ≤ l ≤ 22, всего отражений 96987, независимых отражений 16158 (Rint = 0,0701), число уточняемых параметров 392, GOOF 1,060, R-факторы по F2 > 2σ(F2): R1 = 0,1304, wR2 = 0,2093. Кристалл 1 состоит из тетраэдрических тетрафенилфосфониевых катионов и тиобензолсульфонатных анионов, в которых отрицательный заряд локализован на терминальных атомах серы и кислорода (S-S1,940(3) Å, S=O1,443(5), 1,449(4) Å, S-C 1,775(6) Å).


Ключевые слова


тиобензолсульфонат тетрафенилфосфония; синтез; строение; рентгеноструктурный анализ

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Литература


Wittig G., Geissler G. Zur Reaktions Weise des Pentaphenylphosphorus und Einiger Derivate. Ann., 1953, bd. 580, pp. 44–57.

Zykova A.R. [Synthesis and Structure of Aryl Phosphorus Compounds]. Bulletin of the South Ural State University. Ser. Chemistry. 2020, vol. 12, no. 4, pp. 5–50. (in Russ.). DOI: 10.14529/chem200401

Sharutin V.V., Sharutina O.K., Poddel'sky A.I. Aryl Compounds of Pentavalent Antimony: Syntheses, Reactions, and Structures. Russ. J. Coord. Chem., 2020, vol. 46, no. 10, pp. 663–728. – DOI: 10.1134/S1070328420100012.

Sharutin V.V., Mosunova Т.V. [Synthesis, Structure and Application of Aryl Bismuth Compounds]. Bulletin of the South Ural State University. Ser. Chemistry. 2020, vol. 12, no. 3, pp. 7–66. (in Russ.). DOI: 10.14529/chem200301

Razuvaev G.A., Osanova N.A. [Study of Free-radical Pentaphenylphosphorus]. Dokl. AN SSSR [Report Aademy of Sciences of the USSR], 1955, no. 4(104), pp. 552–554. (in Russ.)

Razuvaev G.A., Osanova N.A, Grigorieva I.K. [Some Heterolytic Reactions of Pentaphenylphosphorus and Pentaphenylantimony]. Izv. AN SSSR. Ser. Khim. [Izv. Academy of Sciences of the USSR. Ser. Chem], 1969, no. 10, pp. 22342237. (in Russ.)

Sharutin V.V. Pentafenil’nye soedineniya fosfora, sur’my, vismuta i ikh proizvodnykh. Vozmozhnosti primeneniya v organicheskom sinteze. Diss. dokt. khim. nauk [Pentaphenyl Compounds of Phosphorus, Antimony, Bismuth and Their Derivatives. Applications in Organic Synthesis. Doct. Sci. Diss. (Chem.)]. Irkutsk, 1995. 257 p.

Sharutin V.V. The Role of Steric Factors in the Processes of Thermal Decomposition of Pentaphenyl Compounds of Phosphorus, Antimony and Bismuth. Arylation of Organoelement and Organic Compounds with Aryl Derivatives of Five-coordinated Bismuth. J. Gen. Chem., 1988, no. 10(58). pp. 23052311.

Sharutin V.V., Senchurin V.S., Sharutina O.K., Boyarkina E.A. Tetraphenylphosphorus carboxylates and sulfonates. Synthesis and structure. J. Gen. Chem., 2009, no. 1(79), pp. 78–87. DOI: 10.1134/S1070363209010125.

Sharutin V.V., Sharutina O.K., Rybakova A.V., Gubanova Yu.O. Synthesis and Structure

of Tetraphenylphosphorus Carboxylates. J. Gen. Chem., 2018, no. 8(88), pp. 1629–1634. DOI: 10.1134/S1070363218080133.

Li J.-S., Liu R.-C., Chi X.-B., Wang G.-C., & Guo Q.-S. Synthesis, Characterization and Structure of Some Arylantimony Ferrocenylacrylates. Inorg. Chim. Acta., 2004, vol. 357, no. 7, pp. 2176–2180. DOI: 10.1016/j.ica.2003.12.012.

Sharutin V.V., Molokova O.V., Sharutina O.K. Synthesis and Structure of Bis(tetraphenylantimony) 1,2-Diphenylethanedione Dioximate Toluene Solvate Ph4SbONC(Ph)С(Ph)ONSbPh4 • 2PhCH3 and Tetraphenylantimony 2-Hydroxy-1,2- diphenylethanone Oximate Ph4SbONC(Ph)CH(Ph)OH. Russ. J. Inorg. Chem., 2013, vol. 58, no. 4, pp. 400–405. DOI10.1134/S0036023613040177.

Ma C., Zhang Q., Sun J., & Zhang R. Syntheses, Characterizations and Crystal Structures of New Organoantimony(V) Complexes with Heterocyclic (S, N) Ligand. J. Organomet. Chem., 2006, vol. 691, no. 11, pp. 2567–2574. DOI: 10.1016/j.jorganchem.2006.01.049.

Arvanitis G.M., Berardini M.E., Acton T.B., & Dumas P.E. Synthesis of Two Tetraphenylantimony Complexes of Pyridine-N-oxides; Crystal Structure of Tetraphenylantimony (2-Mercaptopyridine-N-oxide). Phosphorus, Sulfur Silicon, Relat. Elem., 1993, vol. 82, no. 1–4, pp. 127–135. DOI: 10.1080/10426509308047416.

Sharutin V.V., Sharutina O.K., Senchurin V.S. Tri- and Tetraphenylantimony Propiolates: Syntheses and Structures. Russ. J. Coord. Chem., 2014, vol. 40, no. 2, pp. 109–114. DOI: 10.1134/S1070328414020109.

Sharutin V.V., Sharutina O.K., Senchurin V.S. Tetraphenylantimony Aroxides Ph4SbOAr

(Ar = C6H4C6H7, C6H2(Br2-2,6)( tert -Bu-4), C6H3(NO2)2-2,4, C6H2(Br2-2,6)(NO2-4)): Synthesis and Structure. Russ. J. Inorg. Chem., 2017, vol. 62, no. 3, pp. 295–300. DOI: 10.1134/S0036023617030147.

Sharutin V.V., Sharutina O.K., Gubanova Y.O., Eltsov O.S. Dihydroxybenzoic Acids as Polydentate Ligands in Phenylantimony (V) Complexes. Inorg. Chim. Acta., 2019, vol. 494, pp. 211–215. DOI: 10.1016/j.ica.2019.05.029

Liu R.-C., Ma Y.-Q., Yu L., Li J.-S., Cui J.-R., & Wang R.-Q. Synthesis, Characterization and in vitro Antitumor Activity of Some Arylantimony Ferrocenecarboxylates and Crystal Structures of C5H5FeC5H4CO2SbPh4 and (C5H5FeC5H4CO2)2Sb(4‐CH3C6H4)3. Appl. Organomet. Chem., 2003, vol. 17, no. 9, pp. 662–668. DOI: 10.1002/aoc.491.

Li J.-S., Ma Y.-Q., Cui J.-R., & Wang R.-Q. Synthesis and in vitro Antitumor Activity of Some Tetraphenylantimony Derivatives of exo-7-Oxa-bicyclo[2,2,1]heptane(ene)-3-arylamide-2-acid. Appl. Organomet. Chem. 2001, vol. 15, no. 7, pp. 639–645. DOI: 10.1002/aoc.200.

Quan L., Yin H., Cui J., Hong M., Cui L., Yang M., & Wang D. Synthesis and Crystal Structure of Dinuclear Tetraphenylantimony Carboxylate Derivatives Based on Different Coordination Modes. J. Organomet. Chem., 2009, vol. 694, no. 23, pp. 3683–3687. DOI: 10.1016/j.jorganchem.2009.07.041.

Sharutin V.V., Sharutina O.K., Efremov A.N., Artem'eva E.V. Tri- and Tetraphenylantimony 3,3,3-Trifluoropropanates: Synthesis and Structure. Russ. J. Inorg. Chem., 2019, vol. 64, no. 10, pp. 1229–1234. DOI: 10.1134/S0036023619100139.

Sharutin V.V., Sharutina O.K., Efremov A.N., Artem'eva E.V. Fluorine-Containing Tetraarylantimony Carboxylates: Synthesis and Structure. Russ. J. Inorg. Chem., 2020, vol. 65, no. 4, pp. 502–506. DOI: 10.1134/S0036023620040178.

Sharutin V.V., Sharutina O.K., Bondar’ E.A., Pakusina A.P., Gatilov Yu.V., Adonin N.Yu. [Synthesis of Tetra- and Triaryl-antimony Fluorobenzoates]. Russ. J. Gen. Chem., 2002, vol. 72, no. 3, pp. 419–420. (in Russ.)

Sharutin V.V., Sharutina O.K., Bondar’ E.A., Pakusina A.P., Adonin N.Y., Starichenko V.F., Fukin G.K., Zakharov L.N. Tetraphenylantimony Pentafluorobenzoate and Tetra-p-Tolylantimony Nitrate: Syntheses and Structures. Russ. J. Coord. Chem., 2001, vol. 27, no. 6, pp. 393–397. DOI: 10.1023/a:1011335724711.

Sharutin V.V., Sharutina O.K., Bondar’ E.A., Pakusina A.P., Gatilov Y.V., Adonin N.Y., Starichenko V.F. Tetra- and Triarylantimony Fluorobenzoates: Synthesis and Structures. Russ. J. Coord. Chem., 2002, vol. 28, no. 5, pp. 333–340. DOI: 10.1023/a:1015517216693.

Sharutin V.V., Senchurin V.S., Sharutina O.K., Pakusina A.P., Smirnova S.A. Synthesis and Structure of Tetraphenylantimony 1-Adamantanecarboxylate and Triphenylantimony Bis(1-adamantanecarboxylate). Russ. J. Gen. Chem., 2009, vol. 79, no. 10, pp. 2131–2136. DOI: 10.1134/s1070363209100107.

Sharutin V.V., Sharutina O.K. Tetra-para-tolylantimony Derivatives (4-MeC6H4)4SbX,

X = OC(O)C6H4(NO2-2), OC(O)C≡CPh, ON=CHC6H4(NMe2-4): Synthesis and Structure. Russ. J. Inorg. Chem., 2017, vol. 62, no. 7, pp. 905–909. DOI: 10.1134/s003602361707021x.

Senchurin V.S., Orlenko E.D. [4-Nitrophenylacetates of Tetra- and Tri-(para-tolyl) Antimony. Synthesis and Structural Features]. Bulletin of the South Ural State University. Ser. Chemistry, 2019, vol. 11, no. 2, pp. 66–74. (in Russ.). DOI: 10.14529/chem190207.

Sharutin V.V., Sharutina O.K., Efremov A.N. and Artem’eva E.V. Fluorine-Containing Tetraarylantimony Carboxylates: Synthesis and Structure. Russ. J. Inorg. Chem., 2020, vol. 65, no. 4, pp. 502–506. DOI: 10.1134/S0036023620040178

Senchurin V.S., Sharutin V.V., Sharutina O.K. Phenyl Bismuth(V) Derivatives Ph3Bi[OC6H3(NO2)2-2,5]2 ⋅ 0.5PhH, Ph4BiOC6H3(NO2)2-2,5 and Ph4BiBr: Synthesis and Structure. Russ. J. Inorg. Chem, 2020, vol. 65, no. 3, pp. 323328. DOI: 10.1134/S0036023620030122

Sharutin, V.V. Study of the Crystal Structures of Tetraphenylbismuth Hydrosulfate, Tetraphenylbismuth 2,4-Dinitrobenzenesulfonate, and an Adduct of Tetraphenylbismuth Nitrate with Water. J. Struct. Chem., 2020, vol. 61, no. 5, pp. 734–741. DOI 10.1134/S0022476620050091.

Sharutin V.V., Sharutina O.K., Senchurin V.S. Tetraphenylbismuth(V) Derivatives Ph4BiCl, Ph4BiCl, [Ph4Bi∙DMSO-O][PtBr3∙DMSO-S] and [Ph4Bi]2[PtCl6]: Synthesis and Structure. Russ. J.

Inorg. Chem., 2020, vol. 65, no. 11, pp. 1516–1521. DOI: 10.1134/S0036023620110170.

Razuvaev G.A., Osanova N.A., Brilkina T.G., Zinovjieva T.I., Sharutin V.V. Alkyloxy- and Silyloxy-derivatives of P(V) and Sb(V). J. Organomet. Chem., 1975, vol. 99, no. 1, pp. 93–106.

Zhidkov V.V., Sharutin V.V., Belsky V.K., Magomedova N.S. [Interaction of Pentaphenylphosphorane with Paraform]. J. Gen. Chem., 1995, no. 2(65), pp. 251–256. (in Russ.)

Sharutin V.V., Bychkov V.T., Lebedev V.A., Bochkova R.I., Kuzmin E.A. [Thermal Decomposition of Pentaphenylphosphorus in the Presence of Carbon Dioxide – CO2]. J. Gen. Chem., 1986, no. 2(56), pp. 325–328. (in Russ.)

Bruker. SMART and SAINT-Plus. Versions 5.0. Data Collection and Processing Software for the SMART System. Bruker AXS Inc., Madison, Wisconsin, USA, 1998.

Bruker. SHELXTL/PC. Versions 5.10. An Integrated System for Solving, Refining and Displaying Crystal Structures From Diffraction Data. Bruker AXS Inc., Madison, Wisconsin, USA, 1998.

Dolomanov O.V., Bourhis L.J., Gildea R.J., Howard J.A.K., & Puschmann H. OLEX2: Complete Structure Solution, Refinement and Analysis Program. J. Appl. Cryst., 2009, vol. 42, pp. 339–341. DOI: 10.1107/S0021889808042726.




DOI: http://dx.doi.org/10.14529/10.14529/chem210403

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