T. P. Platonova

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.

Synthesis and structure of bismuth complex [n-Bu4N]2+[Bi2I8 · 2 Me2S=O]2−

Bismuth complex [Bu4N]2+[Bi2I8 · 2Me2S=O]2−(I) was synthesized by reacting tetrabutylammonium iodide with bismuth iodide. In the cations, an N atom has a distorted tetrahedral coordination (CNC angles change in the range from 107.9(5)° to 111.9(5)°). In the centrosymmetric binuclear anion, octahedral bismuth atoms are bound to each other through the bridging (br) iodine atoms (Bi-Ibr, 3.2779(7) Å and 3.3156(9) Å), which are coplanar with four terminal (t) iodine atoms (Bi-It, 2.9392(7) Å and 2.9534(8) Å). Two remaining positions near the bismuth atom are occupied by an iodine atom (Bi-I, 3.0079(8) dimethyl sulfoxide (DMSO) molecule (Bi-O, 2.456(5) Å).

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 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.

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–Obr, 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 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)°.

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.