Synthesis and structure of tetra- and triphenylantimony 2,4,6-trichlorophenoxides

The reaction of pentaphenylantimony with 2,4,6-trichlorophenol or bis(2,4,6-trichlorophenoxy)- triphenylantimony in toluene afforded (2,4,6-trichlorophenoxy)tetraphenylantimony. The reaction of triphenylantimony with tert-butyl hydroperoxide and 2,4,6-trichlorophenol led to the formation of bis(2,4,6-trichlorophenoxy) triphenylantimony; further reaction of the latter with triphenylantimony dichloride provided (2,4,6-trichlorophenoxy)triphenylantimony chloride. According to the XRD data, the antimony atoms in the prepared compounds had distorted trigonal-bipyramidal coordination with electronegative ligands in axial positions.     

Synthesis and structure of triphenylantimony diphthalate

Triphenylantimony diphthalate hydrate (I) has been synthesized by the reaction between triphenylantimony and ortho-phthalic acid in the presence of hydrogen peroxide (molar ratio, 1: 2: 1). According to X-ray diffraction data, the antimony atom in a symmetric molecule of compound I (the SbC₃O₂ coordinating moiety has point group C _2v ) has a trigonal bipyramidal coordination. The OSbO axial angle and the CSbC angles in the equatorial plane are 179.83(12)° and 106.04(9)°, 147.93(18)°, respectively. The bond length are 2.153(2) (Sb-O), and 2.110(4), 2.120(3) Å (Sb-C). Intramolecular Sb…O=C contacts (2.802(3) Å) take place in compound I.     

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.     

Synthesis and structure of tetra- and triphenylbismuth arenesulfonates

Tetraphenylbismuth arenesulfonates were synthesized by the reaction of pentaphenylantimony of-bismuth with triphenylbismuth bis(arenesulfonates). Triphenylbismuth bis(arenesulfonates) were synthesized by the reaction of triphenylbismuth with arenesulfonic acids in the presence of hydrogen peroxide. The crystal structures of the tetraphenylbismuth 2,5-dimethylbenzenesulfonate crystal hydrate (1), tetraphenylbismuth 3-carboxy-4-hydroxybenzenesulfonate (2), and triphenylbismuth bis(2,5-dimethylbenzenesulfonate) (3) were determined by X-ray diffraction analysis. The Bi atom in1 has a tetrahedral coordination (bond angles vary from 106.6(6) to 111.9(10)^o). The Bi coordination observed in2 is intermediate between tetrahedral and trigonal-bipyramidal, and that in structure3 is trigonal-bipyramidal, with the oxygen atoms in the axial positions. The Bi−O bond lengths are 2.19(2) and 2.27(2) Å. In the crystal of2, the anions form an infinite hydrogen-bonded chain. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2350–2354, December, 1999.     

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.     

Synthesis and structures of triphenylantimony oximates

The reactions of triphenylantimony or trimethylantimony with tert-butyl hydroperoxide in the presence of acetone oxime, acetophenone oxime, cyclohexanone oxime, or benzaldehyde oxime afforded monomeric triorganoantimony oximates Ph₃Sb(ON=CMe₂)₂, Ph₃Sb(ON=CMePh)₂, Ph₃Sb[ON=C(CH₂)₅]₂, Ph₃Sb(ON=CHPh)₂, and Me₃Sb(ON=CMe₂)₂ in 87—96% yields. X-ray diffraction analysis demonstrated that Ph₃Sb(ON=CMe₂)₂ and Ph₃Sb(ON=CHPh)₂ have trigonal-bipyramidal structures. An analogous reaction with dimethylglyoxime gave rise to polymeric triphenylantimony dioximate in 96% yield. The reaction with butane-2,3-dione monoxime yielded chelate cyclic bis(triphenylantimony) oxides.     

Synthesis and structure of bis(4-iodophenoxy)triphenylantimony and 4-iodophenoxytetraphenylantimony

Russian Chemical Bulletin - A reaction of triphenylantimony with 4-iodophenol in the presence of hydrogen peroxide furnished bis(4-iodophenoxy)triphenylantimony, which when treated with...     

Synthesis and structure of tetraphenylantimony 1-adamantanecarboxylate and triphenylantimony bis(1-adamantanecarboxylate)

Reaction of pentaphenylantimony with triphenylantimony bis(1-adamantylcarboxylate) yielded the solvate of tetraphenylantimony 1-adamantylcarboxylate with benzene. Triphenylantimony bis(1-adamantylcarboxylate) was prepared from triphenylantimony and 1-adamantylcarboxylic acid in the presence of hydrogen peroxide in ether. X-ray studies showed that in the first and in the second product antimony atom has the distorted trigonal bipyramide coordination (OSbO and CSbO trans-angles are 179.42° and 174.58°, respectively). Sb-O interatomic distances are 2.154 and 2.202 Å, respectively. The carbonyl group oxygen atom is coordinated with the central atom, Sb?O interatomic distances are 2.570 and 3.396 Å, respectively.     

Synthesis,crystal structure,and bioactivity of two triphenylantimony derivatives with benzohydroxamic acid and N-phenylbenzohydroxamic acid

Reaction of triphenylantimony dichloride with benzohydroxamic acid or N-phenylbenzohydroxamic acid in 1?:?1 stoichiometry yielded two new triphenylantimony derivatives formulated as [Ph₃SbL₁L₂] (L₁?=?benzohydroxamato, L₂?=?methoxide, 1; L₁?=?N-phenylbenzohydroxamato, L₂?=?Cl, 2), which have been characterized by FT-IR, NMR spectroscopy, elemental analysis, and melting point. Single-crystal X-ray diffraction analyses for 1 and 2 reveal that the antimony is six-coordinate adopting distorted octahedral geometry with one phenyl and methoxide or chloride in axial positions. In the supramolecular structure, a double-chain is shown for 2 constructed by C–H?···?X (X?=?O, C or π) weak interactions, while 1 exhibits a 1-D-chain structure connected by O–H?···?O and N–H?···?N hydrogen bonds. In vitro antitumor study reveals that 1 and 2 display activities against two human tumor cell lines – A549 and HCT-8. To explore the antitumor activity mechanism, DNA binding properties of 1 and 2 with calf thymus DNA (ct-DNA) have been investigated by fluorescence spectra, indicating that 1 and 2 bind to ct-DNA via intercalation, which could induce the death of cancer cells.     

Synthesis and properties of triphenylantimony(V) dithiolate derivative

Interaction of substituted benzene-1,2-dithiols I–III with triphenylantimony(V) dichloride was studied. As a result of the exchange reaction of 3,6-dichlorobenzene-1,2-dithiol with Ph₃SbCl₂ in the presence of triethylamine triphenylantimony(V) 3,6-dichlorobenzene-1,2-dithiolate IV was obtained. Electrochemical properties of the free dithiols and the complex were explored. According to the cyclic voltammetry, the oxidation of the complex is irreversible and corresponds to one electron transfer with follow-up chemical stage. The antioxidant activity of compounds I–IV was examined in the process of oleic acid autoxidation. A more effective inhibition of the oleic acid oxidation was found at adding dithiol and better protective effect was observed in the presence of Ph₃SbCl₂ compared with the complex IV.     

Synthesis and Structure of Bis(2,4,6-Tribromophenoxy)triphenylantimony

Bis(2,4,6-tribromophenoxy)triphenylantimony was synthesized by reacting triphenylstibine with 2,4,6-tribromophenol in ether in the presence of hydrogen peroxide. Its structure was determined by X-ray diffraction analysis. The coordination polyhedron of the Sb atom is a distorted trigonal bipyramid with the aroxy groups in the axial positions. The bond lengths are Sb(1)–C(Ph) 2.095(4)–2.106(4) Å and Sb(1)–O(1,2) 2.099(3) and 2.092(3) Å. The value of the O(1)SbO(2) axial angle is 177.3(1)°.     

Synthesis of triphenylantimony (hydroxo)diketonates by oxidative methods

Triphenylantimony (hydroxo)acetylacetonate, (hydroxo)trifluoroacetylacetonate, and (hydroxo)pivaloyltrifluoroacetonate were prepared in 85–98 % yields by oxidation of triphenylantimony with hydrogen peroxide ortert-butyl hydroperoxide in the presence of -diketones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1302–1304, July, 1994.The authors would like to thank G. A. Mazurenko and V. L. Shirokii for providing pivaloyltrifluoroacetone and trifluoroacetylacetone.This work was carried out with the financial support of the Russian Foundation for Basic Research (project No. 94-03-08846).     

Synthesis of tetra-2,3-quinolinoporphyrazine and its metal complexes

Tetra-2,3-quinolinoporphyrazine and its complexes with a number of metals were synthesized. The electronic and IR spectra of the compounds obtained, which have typical phthalocyanine character, were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1068–1071, August, 1992.     

Synthesis and crystal structure of tetra- and hexanuclear uranium(IV) complexes with hexadentate compartmental Schiff-base ligands

Treatment of UCl4 with the hexadentate Schiff bases H2Li in thf gave the expected [ULiCl2(thf)] complexes [H2Li=N,N'-bis(3-methoxysalicylidene)-R and R = 2,2-dimethyl-1,3-propanediamine (i= 1), R = 1,3-propanediamine (i= 2), R = 2-amino-benzylamine (i= 3), R = 2-methyl-1,2-propanediamine (i= 4), R = 1,2-phenylenediamine (i= 5)]. The crystal structure of [UL4Cl2(thf)] (4) shows the metal in a quite perfect pentagonal bipyramidal configuration, with the two Cl atoms in apical positions. Reaction of UCl4 with H4Li in pyridine did not afford the mononuclear products [U(H2Li)Cl2(py)x] but gave instead polynuclear complexes [H4Li=N,N'-bis(3-hydroxysalicylidene)-R and R = 1,3-propanediamine (i= 6), R = 2-amino-benzylamine (i= 7) or R = 2-methyl-1,2-propanediamine (i= 8)]. In the presence of H4L6 and H4L7 in pyridine, UCl4 was transformed in a serendipitous and reproducible manner into the tetranuclear U(iv) complexes [Hpy]2[U4(L6)2(H2L6)2Cl6] (6a) and [Hpy]2[U4(L7)2(H2L7)2Cl6][U4(L7)2(H2L7)2Cl4(py)2] (7), respectively. Treatment of UCl4 with [Zn(H2L6)] led to the formation of the neutral compound [U4(L6)2(H2L6)2Cl4(py)2] (6b). The hexanuclear complex [Hpy]2[U6(L8)4Cl10(py)4] (8) was obtained by reaction of UCl4 and H4L8. The centrosymmetric crystal structures of 6a.2HpyCl.2py, 6b.6py, 7.16py and 8.6py illustrate the potential of Schiff bases as associating ligands for the design of polynuclear assemblies.     

Synthesis and characterization of liquid crystalline tetra- and octa-substituted novel phthalocyanines

Methylene-bridged tetra- and octa-(13,17-dioxa nonacosane-15 sulfanyl)-substituted metal free- and Ni(II) phthalocyanines were synthesized from the corresponding phthalonitrile (3, 4) derivatives in the presence of the anhydrous metal salt (NiCl₂) or a strong organic base. The new compounds were characterized by elemental analyses, UV/Vis, IR, NMR and mass spectra. The mesogenic properties of these materials were studied by differential scanning calorimetry (DSC), optical microscopy and X-ray diffraction investigations. X-ray diffraction patterns of the mesophase confirm that tetra- and octa-substituted compounds (3a–b, 4a–b) form hexagonal columnar mesophases (Col_h). We indicated that addition of the methylene-bridged phthalocyanine (Pc) core can either decrease the liquid crystal phase transition temperatures or extend the liquid crystal temperature range to include room temperature. Also, the Pc compounds (3a, 3b, 4a and 4b) are liquid crystals at room temperature. These properties of the Pc complexes provide some advantages such as easily obtaining an ordered film for sensor applications. Computational modelling work was combined with X-ray diffraction investigation to validate the diameter of the phthalocyanine molecule (3b).