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.     

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 and Structure of Triphenylbismuth Bis(Fluorobenzoates)

The reaction between triphenylbismuth, hydrogen peroxide, and 3,4,5-trifluorobenzoic or pentafluorobenzoic acid (molar ratio 1 : 1 : 2, respectively) in ether gave triphenylbismuth bis(3,4,5-trifluorobenzoate) (I) and triphenylbismuth bis(pentafluorobenzoate) (II) in 74 and 89% yields, respectively. The structures of compounds I and II were established by X-ray diffraction. The Bi atoms have a distorted trigonal-bipyramidal coordination with acylate groups in the axial positions. The OBiO angles are 170.2(2)° and 171.5(2)° in I and II, respectively. The Bi–C(Ph)_eq bond lengths vary in the range of 2.187(6)–2.204(5) Å, the Bi–O(acyl) lengths are 2.256(5) Å in I, and 2.281(5) and 2.318(5) Å in II. In the crystals I and II, the Bi and carbonyl O atoms are involved in intramolecular interactions (Bi···O(=C) 2.926(5)–3.176(5) Å), which increase the equatorial CBiC angles on the side of these contacts to 136.2(3)° and 138.6(2)° in I and II, respectively.     

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.     

μ-Oxo-Bis[(arenesulfonato)triphenylantimony]: Synthesis and Structure

-Oxo-bis[(4-methylbenzenesulfonato)triphenylantimony] (I) and -oxo-bis[(2,5-dimethylbenzenesulfonato)triphenylantimony] (II) were synthesized by reacting triphenylstibine Ph₃Sb with tri-p-tolylbismuth bis(4-methylbenzenesulfonate) and tri-p-tolylbismuth bis(2,5-dimethylbenzenesulfonate), respectively, in toluene in the presence of air moisture. According yo X-ray diffraction data, the antimony atoms in the compounds synthesized have a distorted trigonal bipyramidal configuration. The SbOSb angles are equal to 138.5(2)° and 180°, respectively. A bent molecule I contains the Sb(1)···Sb(2) (3.690(1) Å) and Sb···S(1,2) (3.521(2), 3.559(2) Å) intramolecular contacts. In a linear molecule II, the Sb···S distances are equal to 3.438(1) Å.     

Synthesis and Structure of Organoantimony Peroxides

Organoantimony peroxides (Ar₂SbO)₄(O₂)₂ (Ar = Ph, p-Tol) were synthesized by oxidation of triarylantimony with hydrogen peroxide in the presence of nitrosophenol or 4-chlorophenol in an ether solution. X-ray diffraction analysis of peroxides obtained revealed that four antimony atoms have octahedral coordination and are connected via bridging oxygen atoms and two peroxide groups. The C–Sb, Sb–O_br, Sb–OO, and O–O distances are equal to 2.106–2.127, 1.958–1.974, 2.202–2.246, 1.471, 1.470 Å (Ar = Ph) and 2.086–2.139, 1.932–1.983, 2.215–2.289, 1.445–1.466 Å (Ar = p-Tol).     

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.     

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 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.     

Tetra- and triarylantimony pentafluoroand pentachlorophenoxides: Synthesis and structure

2,3,4,5,6-Pentafluorophenoxytetraphenylantimony (I), 2,3,4,5,6-pentachlorophenoxytetraphenylantimony (_II), 2,3,4,5,6-pentafluorophenoxytetra-p-tolylantimony (III), and 2,3,4,5,6-pentachlorophenoxytetra-p-tolylantimony (IV) were synthesized by the reaction of pentaarylantimony (Ar = Ph, p-Tol) with pentafluoro- and pentachlorophenol in toluene. Compounds I–IV were also synthesized with yields of up to 95% from pentaarylantimony and triarylantimony diaroxides. Triarylantimony diaroxides Ph₃Sb(OC₆F₅)₂ (V), Ph₃Sb(OC₆Cl₅)₂ (VI), p-Tol₃Sb(OC₆F₅)₂ (VII), p-Tol₃Sb(OC₆Cl₅)₂ (VIII) were synthesized from triarylantimony, tert-butylhydroperoxide, and phenol in ether. The Sb atoms in compounds I–VIII had a distorted trigonal bipyramidal coordination with electronegative ligands in axial positions.     

Synthesis and structures of organoantimony and organobismuth derivatives of 4-sulfophenol and 2,4-disulfophenol

Tetraphenylbismuth 4-hydroxybenzenesulfonate (I) and tetraphenylantimony 4-hydroxybenzenesulfonate (II) are synthesized in yields up to 80% by the reaction of pentaphenylbismuth and pentaphenylantimony, respectively, with 4-sulfophenol. Compounds I and II are also prepared by the ligand redistribution reaction from pentaphenyl compounds of bismuth and antimony and triphenylbismuth bis(4-hydroxybenzenesulfonate) and triphenylantimony bis(4-hydroxybenzenesulfonate), respectively, in yields up to 87%. The recrystallization of compounds I and II from water gives crystalline hydrates Ph₄BiOSO₂C₆H₄(OH-4) · H₂O (III) and Ph₄SbOSO₂C₆H₄(OH-4) · H₂O (IV). Pentaphenylbismuth and pentaphenylantimony react with 2,4-disulfophenol in acetone, regardless of the ratio of the starting reactants, to form bis(tetraphenylbismuth) 4-hydroxybenzene-1,3-disulfonate (V) and bis(tetraphenylantimony) 4-hydroxybenzene-1,3-disulfonate (VI) in yields up to 74%. According to X-ray diffraction data, coordination of the bismuth atoms in compound I is trigonal-bipyramidal with the axial oxygen atom of the 4-hydroxybenzenesulfonate group (Bi···O 2.764 Å). In compound II, coordination of the Sb atom is tetrahedral (CSbC angles 106.2°–112.3°). In crystal III, the distances between the central atom and the nearest oxygen atoms of the arenesulfonate group and the hydrate water molecule are 3.094 and 3.125 Å, respectively. Crystals V and VI consist of doubly charged anions of 2,4-disulfophenol and several distorted tetrahedral cations of tetraphenylbismuthonium (CBi(1)C, CBi(2)C angles and Bi(1)-C, Bi(2)-C bond lengths vary in the intervals 102.1°–122.7°, 105.4°–114.0° and 2.103–2.230, 2.187–2.209 Å, respectively) and tetraphenylantimonium (CSb(1)C, CSb(2)C angles and Sb(1)-C, Sb(2)-C bond lengths 106.3°–112.2°, 101.3°–122.4° and 2.095–2.110, 2.092–2.123 Å, respectively). The Bi(1) and Sb(2) atoms are coordinated by one of the oxygen atoms of the 2,4-disulfophenol anions (distances Bi(1)···O(3) 2.803, Sb(2)···O(1), 2.704 Å).     

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.     

Bis(1-adamantanecarboxylato)triphenylantimony: Synthesis and structure

Bis(1-adamantanecarboxylato)triphenylantimony Ph₃Sb[OC(O)C₁₀H₁₅]₂ was synthesized in 92% yield by reacting triphenylantimony with 1-adamantanecarboxylic acid in the presence of hydrogen peroxide in diethyl ether. X-ray crystallography shows that the antimony atom has a distorted trigonal-pyramidal coordination with axially positioned oxygen atoms of carboxy groups. The axial angle OSbO and equatorial angles CSbC are 179.93(6)° and 99.90(5)°, 99.90(5)°, and 160.20(9)°, respectively; intramolecular contacts Sb···O(=C) are 2.613(1) Å. Structure data on structurally characterized triarylantimony dicarboxylates are systematized.     

Glycerin and CeCl3·7H2O: a new and efficient recyclable medium for the synthesis of bis(indolyl)methanes

Glycerin and CeCl₃·7H₂O were successfully used in recyclable catalytic system for the synthesis of several bis(indolyl)methanes in good to excellent yields through the reaction of indoles with aldehydes. The method is applicable to aliphatic and aromatic aldehydes, and the mixture of glycerin and CeCl₃·7H₂O can be reused up to five times without special treatment and with comparable yields.     

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 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.     

Tetraphenylantimony Pentafluorobenzoate and Tetra-p-Tolylantimony Nitrate: Syntheses and Structures

The reactions of pentaarylantimony with antimony derivatives Ar₃SbX₂(Ar = Ph or p-Tol and X = OC(O)C₆F₅or NO₃) afford tetraphenylantimony pentafluorobenzoate (Ph₄SbOC(O)C₆F₅) and tetra-p-tolylantimony nitrate (p-Tol₄SbONO₂). The compounds obtained were structurally characterized by X-ray diffraction analysis. The Sb atom in Ph₄SbOC(O)C₆F₅has a distorted trigonal-bipyramidal environment with an axial perfluorobenzoate group. The trigonal-bipyramidal coordination of antimony in p-Tol₄SbONO₂is strongly distorted, with the O atom of the nitrato group lying in the axial plane.     

Synthesis and Structure of μ-Oxobis[(nitrito)triphenylantimony]

Triphenylantimony dibromide was reacted with sodium nitrite in aqueous acetone to obtain -oxobis[(nitrito)triphenylantimony]. According to single-crystal X-ray diffraction data, the Sb atoms in the molecule have a trigonal bipyramidal coordination. The molecule is centrosymmetric, the two Sb atoms are linked with each other by a bridging oxygen atom [the SbOSb angle is 141.8(2)°, and the Sb···Sb distance is 3.7354(5) Å]. The Sb-Obr and Sb-Oterm bond lengths are 1.9768(1) and 2.257(3) Å, and the Sb···O and Sb···N distances are 3.020(4) and 3.070(6) Å, respectively.     

Über eine neue mikrochemische Schnellbestimmungsmethode für Antimon

Zusammenfassung Antimon(III)- und Antimon(V)-Verbindungen lassen sich nach Überführung in Na₃[SbS₄] durch Fällung mit [Cr en₃]Cl₃·3 1/2H₂O als [Cr en₃] [SbS₄]·2 H₂O quantitativ bestimmen. Es wird eine Arbeitsvorschrift angegeben, die es gestattet, in 5 bis 10 ccm Lösung 1 bis 2 mg Sb mit hinreichender Genauigkeit zu bestimmen.

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Summary After being converted to Na₃[SbS₄], antimony(III) and antimony(V) compounds can be determined quantitatively by means of [Cr en₃]Cl₃·3 1/2 H₂O which gives a precipitate of the formula [Cr en₃][SbS₄]·2 H₂O. Directions are given for a technique which allows to determine in 5–10 cc. of solution, 1–2 mg. Sb with sufficient accuracy.

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Résumé On peut doser quantitativement des combinaisons d'antimoine(III) et d'antimoine(V), après les avoir transformé par précipitation avec [Cr en₃]Cl₃· 3 1/2 H₂O en [Cr en₃][SbS₄]·2 H₂O. L'auteur indique une méthode d'analyse, permettant de doser avec une exactitude suffisante 1–2 mg de Sb dans 5–10 ccm de solution.

     

Transition metal complexes with the thiosemicarbazide-based ligands. Part 12. Synthesis,structure and template reaction of ammine [2,4-pentane-dione S-methylisothiosemicarbazonato(2-)] nickel(II) dihydrate

Summary Ni(NO₃)₂·6H₂O reacts with 2,4-pentanedione S-methylisothiosemicarbazonehydrogen iodide (H₂L·HI) in aqueous solution; addition of ammonia then yields [NiL(NH₃)]·2H₂O, the crystal structure of which has been determined. In the square-planar [NiL(NH₃)]·2H₂O complex, the ligand, 2,4-pentanedione S-methylisothio-semicarbazone occupies three coordination sites with the bonds to the central atoms involving the terminal nitrogen atoms of the isothiosemicarbazide fragment [Ni–N(3) 1.831 Å and Ni–N(2) 1.842 Å] and the oxygen of the 2,4-pentanedione moiety [Ni–O 1.844 Å]. The template reaction of [NiL(NH₃)]·2H₂O with 2,4-pentanedione and triethyl orthoformate, HC(OEt)₃, gave, by heating the complexes, NiL¹ (1) (L¹ = dianion of the quadridentate NNNN macrocyclic ligand 2,10-bis(methylthio)-5,7,12,14-tetramethyl-1,3,4,8,9,11 -hexaazacyclotetradeca-2,4,6,9,12,-14-hexaene) and NiL² (2) (L² = dianion of the quadridentate ONNO ligand 3-acetyl-6-thiomethyl-9-methyl-5,7,8-tri-azadodeca-3,6,9-triene-2,11-dione) presents described.