Synthesis and Structure of Tetraphenylantimony Nitrate

The reaction of pentaphenylantimony with triphenylantimony dinitrate in toluene gives tetraphenylantimony nitrate in 99% yield. The X-ray diffraction data show that the antimony atom in the molecule of tetraphenylantimony nitrate has a distorted trigonal-bipyramidal coordination with axial location of the oxygen atom of the nitrate group. The Sb-O, Sb_{a x}, and Sb-C_{e q} bond lengths in two independent molecules of tetraphenylantimony nitrate are 2.498(3), 2.548(2); 2.134(3), 2.138(3); and 2.101(3)-2.112 Å.     

μ-Oxo-Bis(Tetraphenylantimony): Synthesis,Structure, and Reactions

Heating of a solution of pentaphenylantimony in toluene in atmospheric oxygen affords -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 Phenylglyoxylate: Synthesis and Structure

Pentaphenylantimony reacts with phenylglyoxylic acid in toluene to give tetraphenylantimony phenylglyoxylate in 88% yield. X-ray data show that the antimony atom in tetraphenylantimony phenylglyoxylate has the trigonal bipyramidal coordination with the oxygen atom in the axial position. The SbÄC distances are 2.114(4), 2.119(4), 2.142(4), and 2.173(4) Å; SbÄO distance, 2.299(3) Å; and C _a SbO angle, 178.7(1)°.     

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) ?, 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) ?, 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 ?. Original Russian Text ? V.V. Sharutin, V.S. Senchurin, O.A. Fastovets, A.P. Pakusina, O.K. Sharutina, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 5, pp. 373–379.     

Synthesis and Structure of Tetraphenylantimony N,N-Diethyldithiocarbamate

Tetraphenylantimony chloride was reacted with sodium N,N-diethyldithiocarbamate in water to obtain tetraphenylantimony N,N-diethyldithiocarbamate in 98% yield. According to X-ray diffraction data, the configuration of the molecule of tetraphenylantimony diethyldithiocarbamate is distorted octahedron, and the Sb-S bond lengths are 2.705(2) and 2.771(2) Å.     

Tetraphenylantimony perrhenate and tetraphenylantimony chlorate: Syntheses and structures

The reaction of tetraphenylantimony chloride with sodium perrhenate or potassium chlorate yields tetraphenylantimony perrhenate (I) and tetraphenylantimony chlorate (II), respectively. Complex I was also synthesized from pentaphenylantimony and triphenylantimony diperrhenate in toluene. According to X-ray diffraction, crystals I and II consist of almost regular tetrahedral tetraphenylstibonium cations (CSbC, 109.4(2)°–109.5(7)° in I and 109.1(1)°–109.6(1)° in II) and [ReO₄]^? (OreO, 107.6(3)°–113.3(5)°) and [ClO₃]^? (OClO, 96.3(9)°, 116.4(5)°) anions, respectively. The average Sb-C bond lengths (2.094(3) Å in I, 2.097(2) Å in II) are close to the sum of the covalent radii of the Sb and C atoms. The average distances Re-O in complex I (1.672(4) Å) and Cl-O in complex II (1.315 Å) correspond to multiple bonds.     

Synthesis, characterization and crystal structures of tri- and tetraphenylantimony(V) compounds containing arylcarbonyloxy moiety

A series of tri- and tetraphenylantimony(V) compounds containing arylcarbonyloxy moiety have been synthesized and characterized by elemental analysis, IR, and NMR spectroscopy. Attempts to grow crystals led to colorless blocks identified by X-ray diffraction as (ArCOO)₂SbPh₃ or (ArCOO)SbPh₄.     

Synthesis and structure of bis(tetraphenylantimony) malonate

Russian Chemical Bulletin - Bis(tetraphenylantimony) malonate was synthesized by the reaction of tetraphenylantimony bromide with silver malonate (the molar ratio was 2:1) in toluene. According to...     

Reaction of bis(phenylethynyl)itterbium with tetraphenylantimony halides

Phenylethynyl itterbium derivative (PhC≡C)₂Yb(THF)₂ reacts with tetraphenylantimony halides in tetrahydrofuran (THF) at room temperature to form triphenylantimony, phenylacetylene, benzene, and phenylethynylitterbium PhC≡CYbX(THF)₄ and itterbium YbX₂(THF)₄ halides; X = Cl, Br, I. The reduction of the antimony derivative is accompanied with the generation of phenyl and phenylethynyl radicals     

Tetraphenylantimony Diphenacylphosphinate: Synthesis and Structure

Tetraphenylantimony diphenacylphosphinate was synthesized by reacting pentaphenylantimony with diphenacylphosphinic acid or triphenylantimony bis(diphenacylphosphinate) in toluene (with a yield up to 88%). According to X-ray diffraction data, the antimony atom in tetraphenylantimony diphenacylphosphinate molecule has a trigonal bipyramidal coordination to the axial oxygen atom. The four Sb-C and one Sb-O distances and C_axSbO angle are equal to 2.102(2), 2.104(2), 2.104(2), 2.169(2), 2.347(1) Å and 176.69(5)°, respectively.     

Synthesis and Structure of (4-Acetyl-3-hydroxyphenoxy)tetraphenylantimony

Pentaphenylantimony was reacted with 4-acetyl-1,3-dihydroxybenzene in toluene at elevated temperature to obtain (4-acetyl-3-hydroxyphenoxy)tetraphenylantimony in 93% yield. According to X-ray diffraction data, the antimony atom in (4-acetyl-3-hydroxy-phenoxy)tetraphenylantimony has a distorted trigonal-bipyramidal configuration. The Sb-O and Sb-C distances are 2.237(1) and 2.112(1), 2.114(2), 2.118(2), 2.170(2) Å, respectively, and the CSbO angle is 177.86(5)°.     

Synthesis and Structure of Bis(tetraphenylantimony) Tetrafluorophthalate

Oxidation of pentaphenylantimony with atmospheric oxygen in toluene on heating gives -oxo-bis(tetraphenylantimony) (yield 63%). Its reaction with tetrafluorophthalic anhydride gives bis(tetraphenylantimony) tetrafluorophthalate (yield 94%). According to single-crystal X-ray diffraction data, the antimony atoms in the molecule of bis(tetraphenylantimony) tetrafluorophthalate have a distorted trigonal bipyramidal coordination with the following geometries: Sb-O bond lengths 2.357(3) and 2.283(3) Å, Sb-C bond lengths 2.108(4)-2.141(4) and 2.100(5)-2.158(4) Å, and CSbO angles 177.42(14)° and 176.18(14)°.     

Synthesis and structure of tetraphenylantimony cyanamide

The reactions of tetraphenylantimony chloride and bromide with carbamide were used to obtain tetraphenylantimony cyanamide in yields of 52 and 48%, respectively. According to X-ray diffraction data, the antimony atom has a distorted trigonal bipyramidal coordination with axial cyanamide and aryl groups [axial CSbN angle 177.76(7)°, Sb-C 2.107(2)-2.167.2, Sb-N 2.3383(18) Å].     

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).     

Thermodynamic properties of tetraphenylantimony benzophenoxymate in the region of 0–450 K

Heat capacity of tetraphenylantimony benzophenoxymate Ph₄SbONCPh₂ is measured for first time using adiabatic calorimeter in the range from 6K to 350K and differential scanning calorimeter in the range from 330 K to 450 K. In the range of 400–450 K is revealed a melting accompanied with partial decomposition of the substance. Standard thermodynamic functions of crystalline Ph₄SbONCPh₂ in the range from T → 0 K to 440 K are calculated. Enthalpy of combustion of this compound is measured in a combustion calorimeter with isothermal cover and static bomb. Standard thermodynamic formation functions of crystalline Ph₄SbONCPh₂ at 298.15 K are calculated. Fractal dimension D is revealed.     

Synthesis and Structure of New Crystal Modification of Tetraphenylantimony 4-Methylbenzenesulfonate

Tetraphenylantimony arenesulfonates were synthesized by the reaction of pentaphenylantimony with arenesulfonyl chlorides in toluene taken in a molar ratio of 1 : 1 : 2 in air. The structure of tetraphenylantimony 4-methylbenzenesulfonate was determined by X-ray diffraction analysis. The Sb atom has a distorted trigonal-bipyramidal coordination with phenyl and arenesulfonate groups in the axial positions. The Sb–C(Ph)_eq bond lengths vary in the 2.099(2)–2.123(2) Å range, and the Sb–C(41) and Sb–O(1) distances are 2.136(2) and 2.499(1) Å, respectively. The O(1)SbC(4) axial angle is 175.77(5)°.     

Arylation of Aryl- and Diarylbismuth Arenesulfonates with Pentaarylantimony

Pentaarylantimony Ar₃Sb (Ar = Ph, p-Tol) arylates diarylbismuth arylsulfonates Ar₂BiOSO₂Ar' (Ar' = C₆H₄Me-4; C₆H₃Me₂-2,4, C₆H₃Me₂-2,5) in ether at 20°C (48 h) to form triarylbismuth in yields of up to 95%. The second reaction product is tetraarylantimony arenesulfonate. The reaction of pentaphenylantimony with phenylbismuth bis(arenesulfonate) PhBi(OSO₂Ar')₂ under the same conditions leads to formation of diphenylbismuth arenesulfonate and tetraphenylantimony arenesulfonate in yields of up to 90%.     

Synthesis and structure of [(μ4-succinato)hexadecaphenyltetraantimony] triiodide solvate with benzene [(Ph4Sb)2O2CCH2CH2CO2(Ph4Sb)2][I3]2 · 4PhH

Russian Journal of Coordination Chemistry - The reaction of bis(tetraphenylantimony) succinate with iodine in benzene affords [(μ4-succinato) hexadecaphenyltetraantimony] triiodide solvate...     

Synthesis and Structure of Tetra- and Triarylantimony Oximates

Reactions of pentaphenyl- and penta-p-tolylantimony with benzophenone oxime or triarylantimony bis(benzophenone oximate) yield tetraarylantimony benzophenone oximates. Triarylantimony bis(benzophenone oximates) were prepared by oxidative addition from triarylstibine and benzophenone oxime in the presence of hydrogen peroxide. X-ray diffraction analysis was performed to show that benzophenone oxime is a dimer and tetraphenylantimony benzophenone oximate has a trigonal bipyramidal antimony atom and an axial oxime oxygen atom.     

Competing reactions of hydrophenylation and phenylation in tetraphenylantimony chloride methyl acrylate palladium chloride system

A new catalytic reaction of the competing phenylation and hydrophenylation in air of methyl acrylate with tetraphenylantimony chloride in the presence of PdCl₂ (0.04 mol per 1 mol of organometallic compound) in acetonitrile at 50°C for 6 h was studied. The yields of methyl cynnamate and methyl hydrocynnamate were 0.73 and 0.27 mol mol^?1 respectively. The products ratio obtained depends slightly on the process duration, the Ph₄SbCl and methyl acrylate ratio, and the structure of Pd salt [PdCl₂, Pd(OAc)₂, Li₂PdCl₄], but significantly on the nature of a solvent (MeCN > DMF > THF). The use of Ph₄SbCl instead of Ph₄SbBr leads to decrease in the yield of methyl hydrocynnamate to 0.04 mol mol^?1. In the reactions of Ph₄SbX (X = F, I, OAc, O₂CEt) the product is not formed at all.