A. V. Gerasimenko

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).

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.

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

Heating of a solution of pentaphenylantimony in toluene in atmospheric oxygen affords μ-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).

Synthesis and Structure of Diphenoxytriphenylantimony

Diphenoxytriphenylantimony was synthesized via the reaction of triphenylantimony dibromide with sodium phenolate, and its structure was determined using X-ray diffraction analysis. The Sb atom exhibits trigonal bipyramidal coordination. The Sb–C bond lengths are equal to 2.095(2), 2.121(2), and 2.122(2) Å the Sb–O distances and the axial OSbO angle are equal to 2.056(1), 2.046(1) Å and 179.11(5)°, respectively.

Synthesis and Structure of Tri(p-tolyl)antimony Dichloride

Tri(p-tolyl)antimony dichloride was prepared by oxidation of tri(p-tolyl)stibine with chlorine or copper(II) chloride. As found by X-ray diffraction analysis, the antimony atom in tri(p-tolyl)antimony dichloride has the configuration of trigonal bipyramid with axially located chlorine atoms. The Sb-Cl and Sb-C distances are 2.476(2) and 2.104(7) Å, and the CSbC and ClSbCl angles are 120 and 180°, respectively.

Synthesis and Structure of (4-Acetyl-3-hydroxyphenoxy)tetraphenylantimony

Pentaphenylantimony was reacted with 4-acetyl-1,3-dihydroxybenzene in toluene at elevated temperature to obtain (4-acetyl-3-hydroxyphenoxy)tetraphenylantimony in 93% yield. According to X-ray diffraction data, the antimony atom in (4-acetyl-3-hydroxy-phenoxy)tetraphenylantimony has a distorted trigonal-bipyramidal configuration. The Sb-O and Sb-C distances are 2.237(1) and 2.112(1), 2.114(2), 2.118(2), 2.170(2) Å, respectively, and the CSbO angle is 177.86(5)°.

Organoantimony Derivatives of 2,4,6-Tribromophenol

Abstract2,4,6-Tribromophenoxytetraphenylantimony was prepared in 93% yield by the reaction of pentaphenylantimony with bis(2,4,6-tribromophenoxy)triphenylantimony Ph3Sb(OC6H2Br3-2,4,6)2 in toluene at 90°C (1 h). Bis(2,4,6-tribromophenoxy)triphenylantimony, in turn, was prepared by oxidation of triphenyl- stibine with hydrogen peroxide in the presence of 2,4,6-tribromophenol in ether at 20°C (12 h) in 47% yield, with the second reaction product being μ-oxobis[(2,4,6-tribromophenoxy)triphenylantimony] in which the antimony atom, according to single crystal X-ray diffraction, has a trigonal bipyramidal surrounding with the bridging oxygen atom and 2,4,6-tribromophenoxy substituents in the axial positions.

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 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.

Novel Antimony Complexes: [Ph4Sb]4+[Sb4I16]4− · 2Me2C=O and [Ph4Sb]3+[Sb5I18]3−

The [Ph4Sb]4+[Sb4I16]4− · 2Me2C=O and [Ph4Sb]3+[Sb5I18]3− complexes were synthesized by reacting tetraphenylstibonium salts Ph4SbX (X = I, OSO2C6H4Me-4) with antimony triiodide in acetone. According to X-ray diffraction data, their tetra- and pentanuclear anions [Sb4I16]4− and [Sb5I18]3− have cyclic and linear structure, respectively.