A. P. Pakusina

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 Triphenylantimony Dipropionate

Triphenylantimony dipropionate Ph3Sb[OC(O)C2H5]2was prepared by reacting triphenylantimony dibromide with sodium salt of propionic acid in toluene at 90°C. The structure of the compound was determined by X-ray diffraction. The coordination of the Sb atom in the compound is a trigonal bipyramid with the carboxylic groups in the axial positions. The Sb(1)–C(Ph)eqdistances vary in the 2.099(7)–2.135(6) Å range; the Sb(1)–O(1,3) distances are 2.113(5) and 2.109(5) Å, respectively. The value of the O(1)Sb(1)O(3) axial angle is 175.0(2)°.

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.

Tetraphenyl-and tetratolylantimony complexes with N,N-dialkyldithiocarbamate ligands: Synthesis, X-ray diffraction analysis, and 13C and 15N CP/MAS NMR studies

Crystalline tetraphenylantimony and tetratolylantimony complexes with N,N-dialkyldithiocarbamate ligands [Sb(C6H5)4(S2CNR2)] (R = CH3, C2H5, and C3H7 and R2 = (CH2)6) were synthesized by ligand exchange reactions and studied by 13C and 15N CP/MAS NMR spectroscopy. X-ray diffraction analysis revealed that the complex [Sb(n-CH3-C6H4)4{S2CN(C3H7)2}] exists as the single molecular form, while [Sb(C6H5)4{S2CN(CH2)6}] exists as two molecular conformers. The 13C and 15N signals were assigned to the positions of the atoms in the isomeric structures [Sb(C6H5)4{S2CN(CH2)6}] in terms of different degrees of double bonding in the formally single =N-C(S)S-bond.

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).

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.

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).

Tetraphenylantimony(V) hexachloroplatinate, tetrachloroaurate, and hexachlorostannate [Ph4Sb]2+[PtCl6]2−, [Ph4Sb]+[AuCl4]−, and [Ph4Sb]2+[SnCl6]2−: Synthesis and crystal structures

The reactions of tetraphenylantimony with hexachloroplatinic and chloroauric acids in benzene afford bis(tetraphenylantimony) hexachloroplatinate (I) and tetraphenylantimony tetrachloroaurate (II), respectively. Compound II is also synthesized from tetraphenylantimony chloride and chloroauric acid in acetone. Bis(tetraphenylantimony) hexachlorostannate (III) is synthesized from tin dichloride and tetraphenylantimony chloride in acetone or from tin tetrachloride and tetraphenylantimony chloride in benzene. The crystal structures of compounds I–III are determined by X-ray diffraction analysis. The antimony atoms in the [Ph4Sb]+ cations have a distorted tetrahedral coordination (CSbC bond angles range from 105.7(1)° to 118.5(1)° (I), from 106.2(3)° to 114.4(3)° (II), and from 106.0(1)° to 117.1(1)° (III)). The Sb-C bond lengths vary in intervals of 2.094(2)–2.098(2), 2.087(7)–2.111(7), and 2.093–2.100(3) Å, respectively. The coordination of the Pt and Sn atoms in complexes I and III is close to an ideal octahedral coordination with ClPtCl and ClSnCl bond angles of 88.68(2)°–91.32(3)° and 88.84(3)°–91.16(3)°, respectively. The square coordination of the Au atom in complex II is slightly distorted: the Au-Cl bond lengths are 2.266(2)–2.277(2) Å, the ClAuCl bond angles are equal to 89.7(1)°–90.5(1)°, the root-mean-square deviation of the atoms from the coordination plane being 0.004 Å.

Synthesis and Structure of 2- tert -Butylphenoxytetraphenylantimony

Abstract2-tert-Butylphenoxytetraphenylantimony Ph4SbOC6H4(Bu-t)-2 was prepared by the reaction of pentaphenylantimony with 2-tert-butylphenol in toluene at 20°С. 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–CArdistances are 2.143(4) and 1.363(8) Å, respectively. The C(Ph)axSbOAraxial angle is 174.1(2)°, while the SbOC angle is 126.7(4)°.

Synthesis and structure of triarylantimony bis(arenesulfonates)

Triarylantimony bis(arenesulfonates) were prepared by reaction of triarylantimonies with hydrogen peroxide in the presence of arenesulfonic acids. The steric structure of the products was assessed. Triarylantimony bis(arenesulfonates) were reacted with sodium salts to obtain sodium arenesulfonates and the corresponding triarylantimony derivatives.