Reactions of tetraphenylantimony mercaptides

Reactions of tetraphenylantimony mercaptides, Ph₄SbSC₆H₄Y, with electrophilic species in chlorocarbon solutions are reported. With chloromethyl methyl sulphide, allyl halides, sulphenyl halide, acyl halides, halogens, and triphenyltin chloride, ready and complete halide—mercaptide exchanges occur. No allylic rearrangement is found in the reaction with transPhCHCHCH₂Br. In a competition reaction for ClCH₂SMe, Ph₄SbSC₆H₅ was shown to be only slightly (ca. 1.2 times) more reactive than Ph₄SbSC₆H₄OMe-p. The initial sulphur-containing product or reaction with p-toluenesulphonyl chloride, namely the thiosulphonate, p-MeC₆H₄SO₂SC₆H₄Y, reacts further with Ph₄SbSC₆H₄Y to produce the disulphide, (YC₆H₄S)₂. Benzoyl peroxide and Ph₄SbSC₆H₄Y provide PhSbOCOPh and disulphide.     

Thermodynamic properties of tetraphenylantimony 1-adamantanecarboxylate

Journal of Thermal Analysis and Calorimetry - In the present work for the first time, the temperature dependence of the heat capacity $$C_{\text{p}}^{\text{o}}$$ = f(T) of tetraphenylantimony...     

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].     

Synthesis and structure of tetraphenylantimony hydrogenmalonate

Tetraphenylantimony hydrogenmalonate (I) has been prepared via a reaction between equimolar amounts of pentaphenylantimony and malonic acid with a yield of 91%. According to X-ray diffraction data, the antimony atom in a molecule of complex I has a distorted trigonal bipyramidal coordination to the oxygen and carbon atoms in axial positions. The Sb-C_eq, Sb-C_ax, and Sb-O distances equal 2.105(3), 2.107(3), and 2.118(3) Å, 2.148(3) Å, and 2.406(4) Å, respectively, and the C_axSbO_ax angle is 176.91(11)°.     

Synthesis and structure of tetraphenylantimony hydrogen phthalate

Tetraphenylantimony hydrogen phthalate, Ph4SbOC(O)C6H4000H-o, was prepared by the reaction of pentaphenylantimony with phthalic acid. According to the data of X-ray structural analysis, the resulting compound is a trigonal-bipyramidal complex of antimony with three phenyl groups in equatorial positions; the fourth phenyl group and the carboxyl fragment are in axial positions. The CSbO angle is 177.5(1)° the Sb-C(Ph)_eq and Sb-C(Ph)ax distances are 2.099(4)-2.177(4) A and 2.129(4) A, respectively. The H atom of the free carboxyl group and the carbonyl O atom of another carboxylate group form an intramolecular hydrogen bond.DeceasedTranslated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2082–2085, August, 1996.     

The structure of tetraarylantimony halides and tetraphenylantimony isothiocyanate

X-ray diffraction analysis is used to study tetraphenylantimony fluoride (I), tetra-p-tolylantimony (II), and tetraphenylantimony isothiocyanate (III), where Sb atom has a distorted trigonal-bipyramidal coordination. The Sb-C bond lengths in I–III lie a range of 2.102(1)–2.183(1) Å; the Sb-F, Sb-Cl, and Sb-N distances are equal to 2.0530(8) Å, 2.7319(7) Å, and 2.507(2)Å, respectively, in I, II, and III.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 2, 2005, pp. 117–124.Original Russian Text Copyright © 2005 by Sharutin, Sharutina, Pakusina, Smirnova, Pushilin.     

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 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...     

Tri- and tetraphenylantimony propiolates: Syntheses and structures

The reaction of triphenylantimony with propiolic acid in the presence of hydrogen peroxide (molar ratios 1 : 2 : 1 and 1 : 1 : 1) in diethyl ether affords triphenylantimony dipropiolate Ph₃Sb[OC(O)C≡CH]₂ (I) and μ₂-oxobis[(propiolato)triphenylantimony] [Ph₃SbOC(O)C≡CH]₂O (II). Tetraphenylantimony propiolate Ph₄SbOC(O)C≡CH (III) is synthesized from pentaphenylantimony and propiolic or acetylenedicarboxylic acid in toluene. According to the X-ray diffraction data, the crystals of compounds I and III include two types of crystallographically independent molecules (a and b). The antimony atoms in molecules Ia, Ib, II, IIIa, and IIIb have the trigonal-bipyramidal coordination mode with different degrees of distortion. The OSbO and OSbC axial angles are 176.8(2)° (Ia, Ib), 170.17(15)°, 178.78(14)° (II), and 173.2(5)°, 174.4(5)° (IIIa, IIIb). The CSbC equatorial angles lie in the ranges 108.2(3)°–143.1(3)° (I), 109.0(2)°–131.0(2)° (II), and 113.1(4)°–125.4(4)° (III). The SbOSb angle in II is 141.55(19)°. The Sb-C bond lengths are 2.103(8)–2.141(5) (I), 2.105(5)–2.119(5) (II), and 2.076(12)–2.166(13) Å (III). The Sb-O distances increase in a series of I, II, and III: 2.139(6)–2.156(7) (Ia, Ib); 2.206(4), 2.218(3) (II); and 2.338(10), 2.340(10) Å (III).     

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 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)°.     

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     

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)°.     

Catalytic C-phenylation of methyl acrylate with tetraphenylantimony(v) halides and carboxylates

Catalytic C-phenylation of methyl acrylate to methyl cinnamate with the Ph₄SbX complexes (X = F, Cl, Br, OH, OAc, O₂CEt) in the presence of the palladium compounds PdCl₂, Pd(OAc)₂, Pd₂(dba)₃, Pd(Ph₃P)₂Cl₂, and Pd(dppf)Cl₂ (dba is dibenzylideneacetone and dppf is bis(diphenylphosphinoferrocene)) was studied in organic solvents (MeCN, THF, DMF, MeOH, and AcOH). The highest yield of methyl cinnamate (73% based on the starting organometallic compound) was obtained for the Ph₄SbCl—PdCl₂ (1 : 0.04) system in acetonitrile.     

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.     

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.     

Thermodynamics of

Formation of cobalt(II)-thiocyanato complexes in nonionic surfactant solutions of poly(ethylene oxide) type with varying poly(ethylene oxide) chain lengths of 7.5 (Triton X-114), 30 (Triton X-305), and 40 (Triton X-405) has been studied by titration spectrophotometry and calorimetry at 298 K. Data were analyzed by assuming formation of a series of ternary complexes Co(NCS)(n)Y(m)((2-n)+) (Y=surfactant) with an overall formation constant beta(nm). In all the surfactant systems examined, data obtained can be explained well in terms of formation of Co(NCS)(+) and Co(NCS)(2) in an aqueous phase (aq), and Co(NCS)(4)Y(2-) in micelles, and their formation constants, enthalpies, and entropies have been determined. The beta(41)/beta(20) ratio increases and the corresponding enthalpy becomes significantly less negative with an increasing number of ethylene oxide groups. This suggests that micelles of these nonionic surfactants have a heterogeneous inner structure consisting of ethylene oxide and octylphenyl moieties. Indeed, on the basis of molar volumes of ethylene oxide and octylphenyl groups, intrinsic thermodynamic parameters have been extracted for the reaction Co(NCS)(2)(aq)+2NCS(-)(aq)=Co(NCS)(4)Y(2-) (Delta(r)G degrees, Delta(r)H degrees, and Delta(r)S degrees ) at each moiety. The Delta(r)G degrees, Delta(r)H degrees, and Delta(r)S degrees values are -16 kJ mol(-1), -15 kJ mol(-1), and 3 J K(-1) mol(-1), respectively, for the ethylene oxide moiety, and -15 kJ mol(-1), -70 kJ mol(-1), and -183 J K(-1) mol(-1) for octylphenyl. Significantly less negative Delta(r)H degrees and Delta(r)S degrees values for ethylene oxide imply that the hydrogen-bonded network structure of water is extensively formed at the ethylene oxide moiety, and the structure is thus broken around the Co(NCS)(4)(2-) complex with weak hydrogen-bonding ability. Copyright 2001 Academic Press.     

Synthesis and crystal structure of dinuclear tetraphenylantimony carboxylate derivatives based on different coordination modes

Two novel dinuclear tetraorganoantimony carboxylate derivatives were synthesized based on two different coordination modes, in which the environment of one of the two Sb atoms is described as trigonal bipyramid and the other is ascribed to distorted octahedron carrying four phenyl and one benzoate substituent. Structures of compound 1 and 2 were determined by single-crystal X-ray analysis, IR and NMR. Of the two compounds, a novel double-chain structure was shown in compound 1 through C-H?π weak interaction, while compound 2 exhibited a 1D chain by C-H?π weak interaction identically.     

Thermodynamics of carbyne

Published data on the thermodynamic properties of carbyne are analyzed and generalized. The thermodynamic properties of carbyne are compared with the properties of other allotropic modifications of carbon (fullerenes, diamonds, and graphite). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 971–980, June, 2000.     

Bis(tetraphenylantimony) succinate,malate, and tartrate: Syntheses and structures

The reactions of pentaphenylantimony with succinic, malic, and tartaric acids (mole ratio 2: 1) in toluene afford bis(tetraphenylantimony) succinate (I), malate (II), and tartrate (III) in yields of 98, 92, and 94%, respectively. According to the X_ray diffraction analysis results, molecules I and II are centrosymmetric. In compound II, the hydroxy group in the acid residue is disordered over two positions. Crystal III includes two types of crystallographically independent molecules (a and b). The antimony atoms in compounds I, II, IIIa, and IIIb have distorted trigonal bipyramidal coordination modes. The axial angles C_axSbO_ax are 166.80(8)° (I); 174.8(2)° (II); 176.4(4)°, 177.4(3)° (IIIa); and 173.3(4)°, 172.7(4)° (IIIb). The equatorial angles C_eqSbC_eq vary in the ranges 99.3(1)°–154.5(1)° (I); 115.2(2)°–123.3(2)° (II); 115.7(4)°–123.3(4)° 115.2(5)°–125.6(5)° (IIIa); and 107.9(4)°-129.1(4)°, 113.7(4)°-124.8(5)° (IIIb). The Sb-C and Sb-O bonds are 2.138(3)-2.176(3), 2.319(2) Å (I); 2.111(6)–2.163(5), 2.243(4) Å (II); 2.072(13)–2.169(11), 2.252(7), 2.284(7) Å (IIIa); and 2.047(11)–2.190(11), 2.224(7), 2.256(7) Å (IIIb). The intramolecular distances Sb…O=C are 2.528(3) (I); 3.267(7) (II); 3.381(7), 3.436(7) (IIIa); and 3.351(7), 3.162(7) Å (IIIb). For structures I, II, and III, the CIF files are CCDC 929151, 941542, and 941543, respectively.