Tetraphenylbismuth 2,4-Dimethylbenzenesulfonate: Synthesis and Structure

Tetraphenylbismuth 2,4-dimethylbenzenesulfonate was synthesized by reacting pentaphenylbismuth or bromine with diphenylbismuth 2,4-dimethylbenzenesulfonate and its structure was established using X-ray diffraction analysis. The Bi atom has a distorted trigonal bipyramidal coordination. The Bi–C bond lengths are equal to 2.199(4)–2.227(4) Å the Bi–O distance and axial CBiO angle are equal to 2.665(3) Å and 174.2(1)°, respectively.     

Triphenylbismuth Bis(2,4,6-Tribromophenoxide): Synthesis and Structure

A reaction of triphenylbismuth with 2,4,6-tribromophenol and hydrogen peroxide (molar ratio 1 : 2 : 1) in ether affords triphenylbismuth bis(2,4,6-tribromophenoxide). The complex obtained was structurally characterized by X-ray diffraction analysis. The coordination polyhedron of the Bi atom is a trigonal bipyramid with axial aroxy groups. The Bi–C and Bi–O bond lengths are 2.202(4), 2.203(4), 2.212(4) and 2.241(3), 2.245(3) Å, respectively. The intramolecular Bi···Br(1,4) contacts are 3.629(1) and 4.077(1) Å, respectively.     

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.     

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.     

Synthesis and Structure of Tetraphenylantimony Phenoxyacetate and Ethylmalonate Ph4SbOC(O)R (R = CH2OPh and CH2C(O)OC2H5)

Tetraphenylantimony phenoxyacetate (I) was synthesized by reacting pentaphenylantimony with phenoxyacetic acid (at a molar ratio of 1 : 1) in toluene. Tetraphenylantimony ethylmalonate (II) was synthesized from triphenylantimony and malonic ether in the presence of hydrogen peroxide (1 : 1 : 1) in diethyl ether. According to X-ray diffraction data, Sb atoms in compounds I and II have a distorted trigonal bipyramidal coordination to the axial oxygen atoms. The axial OSbC_ax angles and Sb-C_ax distances are, respectively, 176.31(6)° and 2.177(2) Å for I and 179.40(4)° and 2.162(1) Å for II. The Sb-C_eq distances lie in the intervals of 2.108(2)-2.127(2) Å for I and 2.117(1)-2.128(1) Å for II. In compounds I and II, the Sb-O bond lengths are equal to 2.235(1) Å and 2.250(1) Å, respectively, and the intramolecular contacts Sb··· are equal to 3.402(2) Å and 3.282(1) Å, respectively.     

Synthesis and structure of tetraphenylantimony hydrogen phthalate

Tetraphenylantimony hydrogen phthalate, Ph4SbOC(O)C6H4000H-o, was prepared by the reaction of pentaphenylantimony with phthalic acid. According to the data of X-ray structural analysis, the resulting compound is a trigonal-bipyramidal complex of antimony with three phenyl groups in equatorial positions; the fourth phenyl group and the carboxyl fragment are in axial positions. The CSbO angle is 177.5(1)° the Sb-C(Ph)_eq and Sb-C(Ph)ax distances are 2.099(4)-2.177(4) A and 2.129(4) A, respectively. The H atom of the free carboxyl group and the carbonyl O atom of another carboxylate group form an intramolecular hydrogen bond.DeceasedTranslated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2082–2085, August, 1996.     

Synthesis and Structure of Bis(tetraphenylantimony) Tetrafluorophthalate

Oxidation of pentaphenylantimony with atmospheric oxygen in toluene on heating gives -oxo-bis(tetraphenylantimony) (yield 63%). Its reaction with tetrafluorophthalic anhydride gives bis(tetraphenylantimony) tetrafluorophthalate (yield 94%). According to single-crystal X-ray diffraction data, the antimony atoms in the molecule of bis(tetraphenylantimony) tetrafluorophthalate have a distorted trigonal bipyramidal coordination with the following geometries: Sb-O bond lengths 2.357(3) and 2.283(3) Å, Sb-C bond lengths 2.108(4)-2.141(4) and 2.100(5)-2.158(4) Å, and CSbO angles 177.42(14)° and 176.18(14)°.     

Phenylation of Antimony(V) Organic Compounds with Pentaphenylantimony. The Structure of Tetraphenylantimony Chloride

Tetraphenylantimony chloride and bromide were synthesized through the reaction of pentaphenylantimony with diphenylantimony trichloride or tribromide taken at a molar ratio of 2 : 1 in toluene. When the initial compounds were taken at a molar ratio of 1 : 1, triphenylantimony dichloride or dibromide was formed. The phenylation of triphenylantimony sulfate with pentaphenylantimony yielded tetraphenylantimony sulfate. According to the X-ray diffraction data, the antimony atom in the tetraphenylantimony chloride molecule has a distorted trigonal bipyramidal configuration with the chlorine atom in the axial position. The Sb–Cl distance is equal to 2.686(1) and Sb–C distances are equal to 2.113(4) and 2.165(4) Å (av. 2.130 Å).     

Synthesis and Structure of Tri-p-tolylantimony Ditosylate

Tri-p-tolylantimony reacts with p-toluenesulfonic acid in the presence of benzoyl peroxide (1 : 2 : 1 molar ratio) in ether to give tri-p-tolylantimony ditosylate in 91% yield. According to X-ray diffraction data, the central antimony atom has the trigonal bipyramidal coordination with the axial location of the tosyl groups. The Sb-O bond lengths are 2.07(2) and 2.17(2) Å; Sb-C bond lengths, 2.08(3), 2.13(3), and 2.13(3) Å; and OSbO bond angle, 175.6(7)°.