Triarylantimony Dicaroxylates Ar3Sb[OC(O)R]2 (Ar = Ph,p-Tol; R = 2-C4H3O, 3-C5H4N): Synthesis and Structure

Bis(2-furoinate)triphenyl- and tri-p-tolylantimony and bis(3-niacinate)triphenylanitmony were synthesized by reacting triarylantimony (Ar₃Sb; Ar = Ph, p-Tol) with 2-furancarboxylic and 3-pyridinecarboxylic acids in the presence of hydrogen peroxide. According to X-ray diffraction data, Sb atoms have trigonal bipyramidal coordination polyhedra. The Sb–O distances are 2.117(4), 2.137(4) Å; 2.136(2), 2.158(2) Å, and 2.112(1), 2.101(2) Å, the Sb···O distances are 2.866(4), 2.798(4) Å; 2.816(2), 2.774(2) Å, and 3.054(2), 3.168(2) Å, respectively.     

Tetra- and Triarylantimony Fluorobenzoates: Synthesis and Structures

The reactions of pentaarylantimony (Ar₅Sb, where Ar = Ph or p-Tol) with triarylantimony bis(pentafluorobenzoate) and triarylantimony bis(3,4,5-trifluorobenzoate) in toluene afforded tetraarylantimony pentafluoro- and 3,4,5-trifluorobenzoates in up to 90% yields. The starting triarylantimony bis(pentafluorobenzoates) and bis(3,4,5-trifluorobenzoates) were prepared in ether by oxidative addition involving triarylstibine, hydrogen peroxide, and pentafluorobenzoic or 3,4,5-trifluorobenzoic acid, respectively, in up to 98% yields. Tetra-p-tolylantimony pentafluorobenzoate and triphenylantimony bis(pentafluorobenzoate) were structurally characterized by X-ray diffraction analysis. The coordination polyhedron of the Sb atoms is a distorted trigonal bipyramid with axial carboxy groups. In these compounds, the Sb atoms and carbonyl O atoms are linked by intramolecular contacts, which are especially pronounced in the latter complex (the Sb···O(=C) distances are 3.377(3) and 2.943(2), 3.167(2) Å, respectively).     

μ-Oxo-Bis[(Bromo)Tri-m-Tolylantimony]: Synthesis and Structure

-Oxo-bis[(bromo)tri-m-tolylantimony] was synthesized by the reaction of tri-m-tolylstibine with hydrobromic acid in ether in the presence of hydrogen peroxide. The complex was structurally characterized by X-ray diffraction analysis. The coordination polyhedron of the Sb atoms is a distorted trigonal bipyramid with the bromine and the bridging O atoms in the axial positions. The Sb(1)–C(Ph) distances vary from 2.085(9) to 2.111(8) Å. The Sb(1)–Br(1) and Sb(2)–Br(2) bond lengths are 2.739(2) and 2.735(2) Å, respectively; the Sb–O_br distances measure 1.949(1) Å.     

Synthesis and Structure of μ-Peroxo-bis(4-bromophenoxotri-p-tolylantimony)

-Peroxo-bis(4-bromophenoxotri-p-tolylantimony) was synthesized by reacting 4-bromophenol with tri-p-tolylstibine in the presence of hydrogen peroxide. According to X-ray diffraction data, the Sb atoms have trigonal bipyramidal coordination. In the centrosymmetric molecule, the two Sb atoms are joined via bridging peroxo group disordered over two sites. The Sb–O(1,2') bond lengths are equal to 1.999(6) and 2.03(1) Å, the Sb···O(2,1') distances are equal to 2.605(9) and 2.626(5) Å, respectively. The lengths of the terminal Sb–O(3) bonds are 2.093(3) Å.     

Structural Features of Triorganylantimony Dicarboxylates R3Sb[OC(O)R′)]2

Triphenylantimony dibenzoate Ph₃Sb(O₂CPh)₂, triphenylantimony bis(methylbenzoates) Ph₃Sb(O₂CC₆H₄Me-n)₂ (n = 2, 4), and tri-p-tolylantimony bis(trichloacetate) p-Tol₃Sb(O₂CCCl₃)₂, whose Sb atoms have trigonal bipyramidal coordination, were studied using X-ray diffraction analysis. The Sb–O bond lengths are equal to 2.119(2) and 2.144(2); 2.115(2); 2.118(2) and 2.127(2); 2.133(2) Å, the Sb···O(=C) intramolecular contacts are equal to 2.797(2) and 2.698(2); 2.845(2); 2.814(2) and 3.030(2); 3.119(2) Å, respectively. The following correlation was found in the structures of triorganylantimony dicarboxylates: the shorter the Sb···O(=C) distances, the greater the equatorial angle on the side of the intramolecular contacts.     

Synthesis and Structure of Tri-p-tolylantimony Dibromide

Tri(p-tolyl)antimony dibromide is synthesized by the oxidation of tri(p-tolyl)stibine with copper bromide CuBr₂ in acetone. According to the X-ray diffraction analysis data, the antimony atom in tri(p-tolyl)antimony dibromide has the configuration of a trigonal bipyramid with axial bromine atoms. The Sb–Br and Sb–C bond lengths are 2.631(5) and 2.111(4) Å, the CSbC and BrSbBr angles are 120° and 180°, and the intramolecular Br...C(1,2) contacts are 3.374 and 3.517 Å, respectively.     

Synthesis and Structure of 2-tert-Butylphenoxytetraphenylantimony

2-tert-Butylphenoxytetraphenylantimony Ph₄SbOC₆H₄(Bu-t)-2 was prepared by the reaction of pentaphenylantimony with 2-tert-butylphenol in toluene at 20°. The structure of the obtained compound was determined by X-ray diffraction. The Sb atom in this compound has a distorted trigonal-bipyramidal coordination with the aroxy group in the axial position. The Sb–C(Ph)_eqand Sb–C(Ph)_axdistances are 2.111(7)–2.138(7) and 2.180(7) Å the Sb–O and O–C_Ardistances are 2.143(4) and 1.363(8) Å, respectively. The C(Ph)_axSbO_Araxial angle is 174.1(2)°, while the SbOC angle is 126.7(4)°.     

Die Kristallstruktur von Tetrachloräthylencarbonat—Antimon(V)-chlorid,C2Cl4O2CO·SbCl5

Zusammenfassung Die Kristallstruktur des Adduktes Tetrachloräthylencarbonat—Antimon(V)-chlorid, C₂Cl₄O₂CO·SbCl₅ wurde mit Hilfe der Schweratom-Methode aus dreidimensionalen Röntgendaten bestimmt und nach der Methode der kleinsten Quadrate bis zu einemR-Wert von 13,1% verfeinert (Raumgruppe P2₁/n — Nr. 14;a=10,13,b=12,15 undc=12,55 Å, =108°40). Die Elementarzelle enthält 4 Moleküle C₂Cl₄O₂CO· SbCl₅. Das Antimonatom ist oktaedrisch von 5 Chloratomen und dem Carbonylsauerstoffatom des Tetrachloräthylencarbonats umgeben (Sb–Cl 2,28–2,33 und Sb–O 2,40 Å).

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The crystal structure of tetrachloroethylene carbonate antimony(V) chloride, C₂Cl₄O₂CO·SbCl₅

The crystal structure of the adduct tetrachloroethylene carbonate antimony(V)-chloride, C₂Cl₄O₂CO·SbCl₅, has been determined by the heavy-atom method from three-dimensional X-ray data. The refinement of the parameters was carried out by least-squares resulting anR-value of 13.1% (space group P2₁/n — No. 14;a=10.13,b=12.15 andc=12.55 Å, =108°40). The unit cell contains 4 discrete molecules C₂Cl₄O₂CO·SbCl₅. The antimony atom is coordinated octahedrally by 5 chlorine atoms and the carbonyl oxygen atom of tetrachloroethylene carbonate (Sb–Cl 2.28–2.33 and Sb–O 2.40 Å).

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Mit 2 Abbildungen     

Synthesis and Structure of Tetraphenylantimony Oximates Ph4SbON=CRR′ (CRR′ = C6H9−C6H9-2 and R = Ph,R′ = C(O)Ph)

The reaction of pentaphenylantimony and the oxime HON=CRR taken in 1 : 1 molar ratio in toluene gave tetraphenylantimony oximates Ph₄SbON=CRR (CRR = C₆H₉–C₆H₉-2 (I) and R = Ph, R = C(O)Ph (II)). According to X-ray diffraction data, the Sb atoms in I and II have a distorted trigonal-bipyramidal coordination with oximate ligands in the axial positions. The C_axSbO angles are 177.6(1)° in I and 176.58(6)° in II. The Sb–C bond lengths lie in the ranges of 2.120(4)–2.203(4) Å for I and 2.122(2)–2.181(2) Å for II. The Sb–O bond lengths are 2.120(2) Å (I) and 2.166(1) Å (II). The lengths of the intramolecular Sb···N contacts are 2.806(3) and 2.918(2) Å in I and II, respectively.     

Synthesis and Structure of Triphenylantimony Bis(Acetophenoneoximate)

Triphenylantimony bis(acetophenoneoximate) was synthesized by the reaction of triphenylantimony with hydrogen peroxide in the presence of acetophenone oxime (taken in the molar ratio of 1 : 1 : 2) in ether. The structure of the obtained compound was determined by X-ray diffraction. The Sb atom has a distorted trigonal-bipyramidal coordination with the oxime groups in the axial positions. The Sb–C(Ph)_eq bond lengths are 2.110(1)–2.113(1) Å, and the Sb–O distances are 2.058(1) and 2.067(1) Å. The intramolecular Sb(1)···N(1, 2) contacts and O(1)SbO(2) axial angle are 2.990(1), 2.916(1) Å and 172.49(4)°, respectively.     

Synthesis and Structure of N,N-Dimethyldithiocarbamates of Tetraphenylantimony and Tetra-p-tolylantimony

Tetraphenylantimony N,N-dimethyldithiocarbamate (I) and tetra-p-tolylantimony N,N-dimethyldithiocarbamate (II) were synthesized via the reaction of tetraarylantimony chloride Ar₄SbCl (Ar = C₆H₅ or C₆H₄Me-4) with sodium N,N-dimethyldithiocarbamate in water. According to the X-ray diffraction data, the tetraarylantimony N,N-dimethyldithiocarbamate molecules have a distorted octahedral configuration. The Sb–S bond lengths are equal to 2.7158(5) Å, 2.7440(5) Å and 2.761(2) Å, 2.8002(2) Å for I and II, respectively.     

Synthesis and Structure of Tetraphenylantimony 2-Furoinate and Benzoate

Tetraphenylantimony 2-furoinate Ph₄SbOC(O)C₄H₃O is synthesized by the reaction of pentaphenyl-antimony with triphenylantimony bis(2-furoinate). The structure of the compound is determined by X-ray diffraction analysis. The Sb atom in the compound has a distorted trigonal-bipyramidal coordination with the phenyl and 2-furoinate groups in the axial positions. The Sb(1)–C(Ph)_eq distances lie in the 2.119(1)–2.121(1) Å interval; the Sb–O(1) and Sb–C(Ph)_ax bond lengths are equal to 2.273(1) and 2.161(1) Å, respectively; and the Sb(1)···(2) intramolecular contact is 3.234(1) Å.     

Synthesis and Structures of Tetra- and Triarylantimony Oximates

Tetraphenylantimony acetophenoneoximate (I) and tetra-n-tolylantimony 3-nitrobenzaloximate (II) were synthesized by reacting pentaarylantimony with oxime or triarylantimony dioximate in toluene. Tri-n-tolylantimony bis(acetophenoneoximate) (III) and triphenylantimony bis(cyclohexanoneoximate) (IV) were synthesized by reacting triarylantimony with oxime and hydrogen peroxide. The structures of compounds I–IV were determined using X-ray diffraction analysis. The antimony atoms in I–IV are coordinated to the axial oxime groups to form a distorted trigonal bipyramid. The Sb–C(Ph) and Sb–O bond lengths and Sb...N intramolecular contacts in structures I and II lie within 2.114–2.135, 2.137–2.154, and 2.857–2.871 Å, respectively; the respective values in structures III and IV are 2.097–2.112, 2.058–2.080, and 2.779–2.874 Å.     

Synthesis and Structure of New Crystal Modification of Tetraphenylantimony 4-Methylbenzenesulfonate

Tetraphenylantimony arenesulfonates were synthesized by the reaction of pentaphenylantimony with arenesulfonyl chlorides in toluene taken in a molar ratio of 1 : 1 : 2 in air. The structure of tetraphenylantimony 4-methylbenzenesulfonate was determined by X-ray diffraction analysis. The Sb atom has a distorted trigonal-bipyramidal coordination with phenyl and arenesulfonate groups in the axial positions. The Sb–C(Ph)_eq bond lengths vary in the 2.099(2)–2.123(2) Å range, and the Sb–C(41) and Sb–O(1) distances are 2.136(2) and 2.499(1) Å, respectively. The O(1)SbC(4) axial angle is 175.77(5)°.     

Synthesis and structure of μ-oxo-bis-[(2,5-dimethylbenzenesulfonato)tri-p-tolylantimony(v)]

μ-Oxobis[(2,5-dimethylbenzenesulfonato)tri-p-tolylantimony(v)] was prepared by the reaction of 2,5-dimethylbenzesulfonic acid with tri-p-tolylstibine in the presence of hydrogen peroxide. According to X-ray diffraction data, the linear O bridge links two Sb atoms having a trigonal bipyramidal configuration. The 2,5-dimethylbenzenesufonate group and the bridging O atom occupy the axial positions and the three tolyl substituents are equatorial. The Sb(1)−O−Sb(2) and O−Sb−O angles are 180.0(0)° and 177.2(1)°; the Sb−C(Ph)_eq, Sb−O(SO₂Ar), and Sb−μ−O distances are 2.090(5)–2.095(6), 2.258(3), and 1.9361(5), respectively. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2346–2349, December, 1999.     

Synthesis and Structure of Tetra- and Triphenylantimony Organosulfonates

Tetraphenylantimony 2-naphthalenesulfonate (I), tetraphenylantimony phenylmethanesulfonate (II), and bis(tetraphenylantimony) sulfate (III) were synthesized via reaction of pentaphenylantimony with 2-naphthalenesulfonic acid, triphenylantimony bis(phenylmethanesulfonate), and triphenylantimony sulfate, respectively, in toluene. Triphenylantimony bis(phenylmethanesulfonate) (IV) was synthesized from triphenylstibine, phenylmethanesulfonic acid, and hydrogen peroxide (taken in the molar ratio of 1 : 2 : 1). Organoantimony betaine (V) was obtained by reacting triphenylstibine with phenylmethanesulfonyl chloride in the presence of hydrogen peroxide. The structures of the compounds synthesized were determined using X-ray diffraction analysis. The Sb atoms in I–IV have distorted trigonal bipyramidal coordination. The Sb–C and Sb–O distances are equal to 2.100(4)–2.140(3) and 2.644(2) Å in molecule I, 2.105(2)–2.131(2) and 2.699(1) Å in II, 2.096(6)–2.169(6) and 2.101(6), 2.271(3) Å in III, and 2.101(3)–2.102(5) and 2.111(2) Å in IV. In V, the Sb atoms have close tetrahedral (2.105–2.115 Å) and remote (2.65, 3.019 Å) octahedral environment (the oxygen atoms of sulfo group of their own and neighboring molecules). Two betaine molecules are joined through the O atoms of the sulfo groups of bidentate phenylmethanesulfonate ligands to form a centrosymmetrical dimer. The intermolecular C(1)–H(1)···O(1) hydrogen bonds (3.10 Å) are formed that strengthen the dimer.     

Synthesis of Tetra- and Triarylantimony Fluorobenzoates

Pentaarylantimonies Ar₅Sb (Ar = Ph, p-Tol) was reacted with triarylantimony bis(perfluorobenzoate) and bis(3,4,5-trifluorobenzoate) in toluene at elevated temperature to obtain tetraarylantimony fluorobenzoates in 90% yield. Triarylantimony bis(fluorobenzoates) were prepared in an yield of up to 98% from triarylstibine and fluorobenzoic acid by oxidative addition in ether in the presence of hydrogen peroxide.     

Synthesis,structure and reactions of μ-oxobis(arenesulfonatotriarylbismuth)

Hydrolysis of triarylbismuth bis(arenesulfonates) in acetone gives bismuth derivatives of the general formula [Ar₃Bi(OSO₂Ar)]₂O (Ar = Ph, p-Tol; Ar = Ph, C₆H₄Me-4, C₆H₃Me₂-2,4, C₆H₃Me₂-3,4). The structure of -oxobis[(3,4-dimethylbenzenesulfonato)triphenylbismuth] was established by means of X-ray diffraction. The molecule has a linear centrosymmetric structure with the bridging oxygen atom in the inversion center. The bismuth atom has a distorted trigonal bipyramidal coordination with the bridging oxygen atom and the arenesulfonate group in axial positions. The Bi-C and Bi-O_term distances are 2.200(2), 2.204(3), and 2.442(2) Å, and the Bi-O_br distances are 2.067(1) Å.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 9, 2004, pp. 1466–1471.Original Russian Text Copyright © 2004 by Sharutin, Egorova, Sharutina, Ivanenko, Pavlushkina, Gerasimenko, Pushilin.This revised version was published online in April 2005 with a corrected cover date.     

Synthesis and Structure of Tetraphenylantimony Nitrite

Tetraphenylantimony nitrite was synthesized by reacting pentaphenylantimony with triphenylantimony dinitrite at a molar ratio of 1 : 1 in toluene, and its structure was determined using X-ray diffraction analysis. The Sb atom is coordinated to the oxygen atom of the axial nitrite group to form a trigonal bipyramid. The Sb–C(Ph)_eq distances vary within the 2.103–2.111(3) Å range, and the S–O(1) and Sb–C(41) bond lengths are equal to 2.386(3) and 2.156(3) Å, respectively. The Sb...N distance and the axial C(41)SbO(1) angle are equal to 3.133(4) Å and 174.7(1)°, respectively.     

μ-Oxo-Bis(Tetraphenylantimony): Synthesis,Structure, and Reactions

Heating of a solution of pentaphenylantimony in toluene in atmospheric oxygen affords -oxo-bis(tetraphenylantimony) (I) in a 63% yield. The latter compound can be converted to bis(tetraphenylantimony) carbonate or phthalate by the action of carbon dioxide or phthalic anhydride, respectively. According to X-ray diffraction data, the antimony atoms in compound Ihave a distorted trigonal-bipyramidal coordination (Sb–O 2.0050(4) Å, the SbOSb angle 151.71(9)°). The molecule of bis(tetraphenylantimony) phthalate is composed of two equal fragments, and its Sb atoms also have trigonal-bipyramidal coordination (Sb–O 2.2421(8) Å; Sb–C 2.176(1), 2.115(1), 2.130(1), and 2.137(1) Å).