Synthesis and structure of antimony complexes [Ph3AmP] 2 + [Sb2I8 · 2DMSO]2−, [Ph3PrP] 2 + [Sb2I8 · C4H8O2]2−, and [(HOCH2CH2)3NH] 4 + [Sb4I16]4−

The reaction of equimolar amounts of triphenylamyl- and triphenylpropylphosphonium iodides and triethanolammonium iodide with antimony iodide in dimethyl sulfoxide, dioxane, or acetone gave complexes [Ph₃AmP] ₂ ⁺ [Sb₂I₈ · 2DMSO]^2?, [Ph₃PrP] ₂ ⁺ [Sb₂I₈ · C₄H₈O₂]^2?, and [(HOCH₂CH₂)₃NH] ₄ ⁺ [Sb₄I₁₆]^4?, the structure of which was established by X-ray diffraction analysis. The cations of all complexes have slightly distorted tetrahedral structure, and the antimony atoms in the anions are hexacoordinated. The crystals of the complexes have intra- and intermolecular contacts, which form the structure.     

Synthesis and structure of <Emphasis Type="Italic">cis</Emphasis>-dichloro(triphenylstibine)(dimethylsulfoxide)platinum(II)

The platinum molecular complex cis-Cl₂(Ph₃Sb)(Me₂S=O)Pt (I) was synthesized by the reaction of tetraphenylstibonium chloride with potassium tetrachloroplatinate in dimethyl sulfoxide. The crystal structure of square-planar complex I was determined by X-ray crystallography. The complex contains, in addition to chlorine atoms, triphenylstibine and DMSO molecules coordinated to the central atom. The bond lengths Pt-Cl, Pt-S, and Pt-Sb are 2.308(1), 2.350(1), 2.195(1), and 2.5118(4) Å, respectively. The compound is the first example of mixed-ligand platinum(II) complex in which the coordination sphere of the central atom contains, along with dimethyl sulfoxide ligand, a tertiary stibine ligand.     

Synthesis and structural features of tris(5-bromo-2-methoxyphenyl)antimony bis (cyclopropanecarboxylate)

Reaction of tris(5-bromo-2-methoxyphenyl)antimony with cyclopropanecarboxylic acid in the presence of hydrogen peroxide (1:2:1 mol) results in tris(5-bromo-2-methoxyphenyl)antimony bis(cyclopropanecarboxylate) I. The structure of the resulting complex was proved by the XRD analysis.     

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).     

Synthesis and structure of tris(4-<Emphasis Type="Italic">N,N</Emphasis>-dimethylaminophenyl) antimony(V) dicarboxylates and diaroxides

Tris(4-N,N-dimethylaminophenyl)antimony dicarboxylates (4-Me₂NC₆H₄)₃Sb[OC(O)R]₂ (R = C₆H₄Me-2 (I), C₆H₄Me-4 (II), CH=CHPh (III)), (4-Me₂NC₆H₄)₃Sb[OC(O)C(O)O] (IV), and (4-Me₂NC₆H₄)₃Sb[OC(O)C₆Cl₄C(O)O] (V)) and tris(4-N,N-dimethylaminophenyl)antimony diaroxides (4-Me₂NC₆H₄)₃Sb(OAr)₂ (Ar = Ph (VI), C₆H₂Br₃-2,4,6 (VII), and C₆H₃Me₂-2,6 (VIII)) have been synthesized by the reaction of tris(4-N,N-dimethylaminophenyl)antimony in ether with carboxylic acids or phenols in the presence of hydrogen peroxide. According to X-ray diffraction analysis data, the Sb atoms in compounds I and VII have a distorted trigonal-bipyramidal coordination, and the axial OSbO angles are 175.4(1)° and 177.9(3)°, respectively. The Sb-O bond lengths are 2.133(3) and 2.142(2) Å in compound I and 2.089(5) Å in compound VII.     

Reactions of triphenylbenzylphosphonium and tetraphenylstibonium chlorides with potassium tetrachloroplatinates in dimethylsulfoxide

Platinum complexes [Ph₃PhCH₂P]⁺[(Me₂S=O)PtCl₃]^? I and cis-Cl₂(Ph₃Sb)(Me₂S=O)Pt II were synthesized by reaction of triphenylbenzylphosphonium and tetraphenylstibonium chlorides with potassium tetrachloroplatinate in DMSO. Crystal I is formed by triphenylbenzylphosphonium tetrahedral cations [P-C_Ph 1.791(4)-1.795(4) Å, P-C_Alk 1.811(4) Å; CPC 107.57(18)°-111.46(17)°] and by square anions [(Me₂S=O)PtCl₃]^? [Pt-Cl 2.3236(11), 2.2981(12), 2.2977(11) Å; Pt-S 2.1950(10) Å; trans-angles SPtCl 177.51(4)°, ClPtCl 178.74(4)°]. In a square-planar complex II [trans-angles SPtCl 178.01(6)°, ClPtSb 177.96(4)°] with central platinum atom the chlorine atoms [Pt-Cl 2.308(1), 2.350(1) Å], triphenylstibine [Pt-Sb 2.5118(4) Å] and dimethyl sulfoxide [Pt-S 2.195(1) Å] molecules are coordinated. Compound II is a first example of mixed ligand complex of platinum(II), where in the coordination sphere of central atom the tertiary stibine is present along with DMSO ligand.     

Synthesis and structure of tetra-p-tolylantimony complexes [(4-MeC6H4)4Sb] 2 + [Hg2I6]2−, [(4-MeC6H4)4Sb] 2 + [HgI4]2−, [(4-MeC6H4)4Sb] 3 + [Sb3I12]2−, and [(4-MeC6H4)4Sb]+[ReO4]−

Complexes [(4-MeC₆H₄)₄Sb] ₂ ⁺ [Hg₂I₆]^2? (I), [(4-MeC₆H₄)₄Sb] ₂ ⁺ [HgI₄]^2? (II), [(4-MeC₆H₄)₄Sb] ₃ ⁺ [Sb₃I₁₂]^2? (III), were synthesized by reactions of tetra-p-tolylantimony iodide with mercury iodide and antimony iodide, respectively. Tetra-p-tolylantimony perrhenate [(4-MeC₆H₄)₄Sb]⁺[ReO₄]^? (IV) was prepared from tetra-p-tolylantimony chloride and sodium perrhenate in acetone. Crystal structures of complexes I, II, and IV were determined by X-ray crystallography. Mercury and rhenium atoms have tetrahedral coordinations in these complexes. The Hg-I and Re-O distances in the structures of I, II, and IV vary within 2.7719(13)–2.7908(12)Å, 2.7028(3)–2.9163(3) Å, and 1.693(3)–1.744(3) Å, respectively. Antimony atoms in two crystallographically independent trinuclear centrosymmetric [Sb₃I₁₂]^2? anions of complex III have an octahedral environment. Each terminal SbI₃ fragment (Sb-I_t, 2.8265(9)–2.8333(10)Å) is bound to the central atom through tree bridging iodine atoms (Sb(2)-I_br, 3.2275(9)–3.3620(10)Å). The distances between the central Sb atom and bridging iodine atoms are much shorter (Sb(1)-I_br, 3.0153(6)–3.0316(6) Å; Sb(3)-I_br, 2.9926(6)–3.0074(6) Å).     

Synthesis and structure of [Ph3MeP]3[Sb3I12]·Me2C=O, [Ph3MeP]3[Sb2I9], [Ph3MeP]2[SbI5], and [Ph3MeP]3[Sb3I12] antimony complexes

Complexes [Ph₃MeP]₃[Sb₃I₁₂]Me₂C=O (I), [Ph₃MeP]₃[Sb₂I₉] (II), and [Ph₃MeP]₂[SbI₅] (III) were obtained via the reaction of triphenylphosphonium iodide with antimony triiodide in acetone in 1:1, 3:2 and 2:1 molar ratios. Reaction of the complex III with antimony triiodide (1:1) affords [Ph₃MeP]₃[Sb₃I₁₂] (IV). The structure of the obtained complexes was confirmed by X-ray analysis.     

Reaction between octanetetraone-2,4,5,7 and pentaphenylantimony

Ph₄Sb[OC(Me)CHC(O)(O)CCH(Me)CO]SbPh₄, a binuclear chelate complex, has been synthesized by a reaction between pentaphenylantimony and octanetetraone-2,4,5,7 (2: 1 mol/mol) in toluene. The Sb(1,2) atoms each have a distorted octahedral coordination, the CSbC and CSbO trans-angles lie within a range of 158.3(8)°–169.1(9)°, and the Sb-C bond lengths are 2.06(2)–2.25(2)Å. The two six-membered [SbO₂C₃] chelate rings have the following distances (Å): Sb-O, 2.25(1)–2.29(1); O-C, 1.20(2)–1.32(2); C-C, 1.32(3)–1.53(3).     

Synthesis and structure of tetraphenylantimony and triphenylantimony 4-oxybenzoates

Solvate Ph₃Sb[OC(O)C₆H₄(OH-4)]₂ · 1/2Et₂O (I) has been synthesized by the reaction between triphenylantimony and 4-oxybenzoic acid in the presence of hydrogen peroxide in diethyl ether. Tetraphenylantimony 4-oxybenzoate, which crystallizes from DMSO in the form of solvate Ph₄SbOC(O)C₆H₄(OH-4) · DMSO (II), has been synthesized from pentaphenylantimony and triphenylantimony bis(4-oxybenzoate) or 4-oxybenzoic acid. According to X-ray diffraction data, an antimony atom in molecules of compounds I and II has a trigonal bipyramidal coordination. Crystals of compound I contain two crystallographically independent types of molecules (A and B). The Sb-C and Sb-O distances, the equatorial CSbC and axial OSbO angles are, respectively, 2.083(9)–2.103(8)Å; 2.068(5), 2.128(5)Å; 117.6(3)°–124.2(3)° and 171.5(2)° (IA); 2.103(9)–2.135(8)Å; 2.086(5), 2.154(6)Å;110.2(3)°–138.0(4)° and 174.8(2)° (IB). In compound II, Sb-C is 2.117(2)–2.175(2) Å, Sb-O is 2.247(2) Å, and C_eqSbC_eq and OSbC_ax angles are 110.89(9)°–133.30(9)° and 177.05(7)°, respectively. The Sb…O=C intramolecular contacts are 3.151(7), 3.153(8) Å (IA), 2.985(8), 3.008(9) Å (IB), and 2.975(5) Å (II). Molecules IA and IB are conformation isomers, which differ from each other by the arrangement of carboxyl groups with respect to the equatorial plane.