O. K. Sharutina

REACTIONS OF PENTAPHENYLANTIMONY WITH DICARBOXYLIC ACIDS

Abstract Interaction of pentaphenylantimony with dicarboxylic acids (mole ratio 1:1 or 2:1) in toluene or dioxane leads to formation of acyloxytetraphenyl derivatives of antimony(V) with 87–99% yield. The studies of two of the products, tetraphenylantimonium maleinate and bis(tetraphenyl) antimonium maleinate, were determined by an X-ray diffraction study.

Synthesis and structure of platinum complexes [Ph 4 P] + [PtCl 3 (DMSO)] − and [Ph 4 P] + [PtCl 5 (DMSO)] −

The reaction of tetraphenylphosphonium chloride with an equimolar amount of potassium tetrachloroplatinate or hexachloroplatinic acid in dimethyl sulfoxide gave the complexes [Ph4P]+[PtCl3(DMSO)]− (I) and [Ph4P]+[PtCl5(DMSO)]− (II), respectively. The phosphorus atoms in the cations have tetrahedral environment, the CPC angles and P-C distances 105.63(13)°–112.13(14)°, 1.795(3)–1.797(3) Å I) and 105.7(3)°–112.9(3)°, 1.783(7)–1.791(6) Å II). The platinum coordination polyhedra in the anions [PtCl3(DMSO)]− and [PtCl5(DMSO)]− are distorted square (Pt-S, 2.1937(8); Pt-Cl, 2.2894(10)–2.3024(10) Å; trans-angles: SPtCl, 177.38(4)°; ClPtCl, 175.40(4)°) and octahedron (Pt-S 2.291(2) Å; Pt-Cl, 2.312(2)–2.334(2) Å, trans-angles: SPtCl, 178.28(9)°; ClPtCl, 178.80(9)° and 178.88(8)°).

Synthesis and structure of the rhodium complex [Ph3MeP][RhBr4(DMSO)2-trans]

The ionic complex, methyltriphenylphosphonium(I) trans-bis(dimethylsulfoxido)tetrabromorhodiate, was prepared by the reaction of sodium hexabromorhodiate with methyltriphenylphosphonium bromide in dimethyl sulfoxide and studied by X-ray diffraction. The phosphorus atom in the [Ph3MeP]+ cation has an almost undistorted tetragonal coordination (the CPC angles are 108.3(2)°–110.5(2)°, the P-C bonds are 1.779(6)–1.798(4) Å). In the octahedral complex anion [RhBr4(DMSO)2-trans]−, the dimethyl sulfoxide ligands are coordinated by the sulfur atoms (Rh-S, 2.344(1), 2.336(1); Rh-Br, 2.4839(7)–2.4934(7) Å; SRhS, 179.56(7)°; trans-BrRhBr, 179.30(3)°, 179.56(7)°) (CIF file CCDC no. 978748).

Tris(4-fluorophenyl)antimony dicarboxylates (4-FC6H4)3Sb[OC(O)R]2 (R = C10H15 or cyclo-C3H5): Synthesis and structure

Tris(4-fluorophenyl)antimony dicarboxylates (4-FC6H4)3Sb[OC(O)R]2, where R = C10H15 (I) or cyclo-C3H5 (II), have been synthesized by the reaction between tris(4-fluorophenyl)antimony and adamantanecarboxylic or cyclopropanecarboxylic acids in ether in the presence of tert-butyl hydroperoxide with a high yield. The antimony atoms in complexes I and II have a distorted trigonal bipyramidal coordination to the carboxylate ligands in axial positions (OSbO angles are 174.02(10)° (I) and 176.53(5)° (II)). The Sb-O and Sb-Ceqv bond lengths are 2.120(3), 2.121(2), and 2.110(3)-2.117(3) Å (I), 2.147(1), 2.122(1), and 2.120(3)-2.123(2) Å (II). Molecules contain intramolecular contacts between the antimony atom and the carbonyl oxygen atom (2.740(3), 2.867(4) Å (I); 2.694(3), 2.773(4) Å (II)). The structural organization in a crystal of complex I is due to weak intermolecular hydrogen bonds H···F (2.42-2.66 Å). Complex II involves the intermolecular contacts H···F (2.63 Å) and H···O=C (2.50 Å).

Synthesis and structure of tris(4-fluorophenyl)antimony dicarboxylates

The interaction of tris(4-fluorophenyl)antimony with chloroacetic, 4-nitrophenylacetic, and benzoic acids in diethyl ether in the presence of tert-butyl hydroperoxide has yielded tris(4-fluorophenyl)antimony dicarboxylates, their Sb atoms bearing distorted trigonal bipyramid coordination with the carboxylate ligands in the axial positions. The intramolecular contacts between Sb atom and carbonyl O atom are formed in the molecules of the products. Their crystal packing is determined by weak intermolecular hydrogen bonds of the H···F and H···O=C types.

Tetraphenylantimony aroxides Ph4SbOAr (Ar = C6H4C6H7, C6H2(Br2-2,6)(tert-Bu-4), C6H3(NO2)2-2,4, C6H2(Br2-2,6)(NO2-4)): Synthesis and structure

Tetraphenylantimony aroxides Ph4SbOAr, where Ar = C6H4C6H7 (I), C6H2(Br2-2,6)(tert-Bu-4) (II), C6H2(Br2-2,6)(NO2-4) (III), and C6H3(NO2)2-2,4 (IV), have been synthesized by the reaction of pentaphenylantimony with 4-cyclohexadienylphenol, 2,6-dibromo-4-tert-butylphenol, 2,6-dibromo-4-nitrophenol, and 2,4-dinitrophenol. The antimony atoms in molecules of complexes I–IV have a differently distorted trigonal bipyramidal coordination to the oxygen atoms of aroxy groups in axial positions. The OSbС angles are 177.63(13)° (I), 174.29(7)° (II), 177.8(6)° (III), and 174.01(7)° (IV). The Sb–O bond length is 2.117(3) Å (I), 2.2613(15) Å (II), 2.409(11) Å (III), and 2.4296(15) Å (IV).

Osmium complexes [Ph4Sb · DMSO]2[OsBr6] and [p-Tol4Sb · DMSO][p-Tol4Sb][OsBr6]: Synthesis and structure

The ionic complexes [Ph4Sb · DMSO]2[OsBr6] (I) and [p-Tol4Sb · DMSO][p-Tol4Sb][OsBr6] (II) have been synthesized by the reaction between sodium hexabromoosmate and tetraphenyl- or tetra-para-tolylstibonium bromide in dimethyl sulfoxide (DMSO). According to X-ray diffraction data, the antimony atoms in [Ph4Sb · DMSO]+ and [p-Tol4Sb · DMSO]+ cations have a distorted trigonal bipyramidal coordination, and the pseudo-axial CSbO and pseudo-equatorial СSbС angles are 173.7(2)°, 172.8(3)° and 111.3(2)°‒121.8(2)°, 107.4(3)°‒120.3(3)°, respectively. In the tetrahedral [p-Tol4Sb]+ cation, the СSbС angles are 106.1(4)°‒111.3(4)°. In the octahedral [OsBr6]2‒ anions, the Os‒Br bond lengths are 2.4765(6)‒2.4981(6) Å (I) and 2.4795(11)‒2.5063(11) Å (II); the trans-BrOsBr angles are 180.00(2)° (I) and 178.83(4)°‒179.34(4)° (II).

Synthesis and structure of osmium complexes: [Ph4Sb]2+ [OsCl6]2–, and [p-Tol4Sb]2+[OsCl6]2—

The reaction of sodium hexachloroosmate with tetraphenyl- or tetra(para-tolyl)stibonium chloride in dimethyl sulfoxide gave the complexes [Ph4Sb]2[OsCl6] (I) and [p-Tol4Sb]2[OsCl6] (II). According to X-ray diffraction data, the CSbC angles in the tetrahedral cations [Ph4Sb]+ and [p-Tol4Sb]+ are 105.97(17)°–117.98(16)° in I and 103.1(3)°–118.0(2)° in II; the Sb–C bond lengths vary in the ranges of 2.090(4)–2.104(4) Å (I) and 2.086(6)–2.107(7) Å (II). In the octahedral anions [OsCl6]2–, the Os–Cl bond lengths are 2.3364(10)–2.3435(12) Å (I) and 2.3159(16)–2.3361(19) Å (II) (CIF files CCDC no. 1000137 (I), 1010809 (II)).

New preparation method of chlorotriphenylantimony aryloxides Ph3SbCl(OAr)

The reaction of bis(2,6-dichlorophenoxo)triphenylantimony with triphenylantimony dichloride gave chloro(2,6-dichlorophenoxo)triphenylantimony Ph3SbCl(OC6H3Cl2-2,6) (I). 2,6-Dichlorophenoxotetraphenylantimony Ph4Sb(OC6H3Cl2-2,6) (II) was prepared from pentaphenylantimony and bis(2,6- dichlorophenoxo)triphenylantimony. According to X-ray diffraction data, the antimony atoms in I and II have a distorted trigonal-bipyramidal coordination with the following axial: OSbCl, 179.59(5)° (I); CSbO, 178.20(14)° (II); the equatorial angles are 115.72(9)°–124.87(10)° (I) and 111.43(18)°–123.18(19)° (II); the equatorial bond lengths are Sb–C, 2.099(3)–2.111(2) Å (I), 2.111(4)–2.122(5) Å (II); and the axial bond lengths are Sb–Cl, 2.4740(7) Å; Sb–O, 2.0802(16) Å (I); Sb–O, 2.237(3) Å; and Sb–C, 2.167(4) Å (II) (CIF files CCDC no. 998625 for I and no. 1010553 for II).

Synthesis and structure of iridium complexes [Ph3PR][trans-IrCl4(DMSO)2]

The reaction of sodium chloroiridate with acetonyl-, cyanomethyl-, and 2-butenyltriphenylphosphonium chloride in dimethyl sulfoxide was used to synthesize ionic iridium complexes [Ph3PR][trans-IrCl4(DMSO)2] (R = CH2C(O)Me, CH2CN, CH2CH=CHMe). The phosphorus atoms in the [Ph3RP]+ cations have a slightly distorted tetrahedral coordination. The dimethyl sulfoxide ligand in the octahedral anions [trans-IrCl4(DMSO)2] is coordinated to metal via sulfur atoms.