Complex Tellurium Salts with Supramolecular Bidimensional Lattices: Synthesis and X‐ray Characterization of (2‐Br‐C5NH5)2[TeX6] (X = Cl,Br)

The reaction of tellurium(IV) tetrahalides with hydrochloric and hydrobromic acid leads to the formation of (H₃O)₂[TeX₆], which reacts subsequently with (2‐Br‐C₅NH₅)⁺X^‐ to afford (2‐Br‐C₅NH₅)₂[TeCl₆] ( 1 ) and (2‐Br‐C₅NH₅)₂[TeBr₆] ( 2 ). The structure of the complex salts were analysed by X‐ray diffractometry affording the centrosymmetric space groups P2₁/n (monoclinic, 1 ) and P1¯ (triclinic, 2 ). Interionic hydrogen bondings hold their lattices in bidimensional supramolecular arrays not yet described in the literature. The lone electron pair of the AX₆E‐system of the hexahalotellurates [TeX₆]^2‐ (X = Cl, Br) seems to be fully delocalized since only small octahedral deviations were observed for the anionic species. The structures of the title compounds were refined with the Te atoms occupying sites with full point symmetry, approximately m3¯m. In both cases the Te atoms enclose centers of inversion and the octahedrally dynamic structures are enforced and stabilized along the supramolecular lattices by the crystal field of the 2‐Br‐pyridinium cations.     

Weak Interionic Interactions in 2‐Haloimidazolium Hexahalotellurates(IV) [1]

The 2‐haloimidazolium salts [C₁₁H₂₀N₂X]X [ 1 ; X = Cl ( a ), Br ( b )] react with TeX₄ to give the salts [C₁₁H₂₀N₂X]₂[TeX₆] [ 2 ; X = Cl ( a ), Br ( b )]. The crystal structure analyses of 2a and 2b · CH₂Cl₂ reveal the presence of ionic pairs linked by weak halogen to halogen interactions.     

Diacyltelluride: Synthesen durch Reaktionen von Acylchloriden mit Bis(trialkylsilyl)telluriden; Strukturbestimmungen an Di(1-adamantoyl)tellurid und Adamantancarbonsäureanhydrid

Diacyltellurides: Synthesis by Reactions of Acyl Chlorides with Bis(trialkylsilyl)tellurides. Structure Determinations of Di(1-adamantoyl)telluride and Adamantanecarbonic Anhydride Bis(isopropyldimethylsilyl)telluride ( 1 ) is prepared from tellurium with lithiumtriethylhydridoborate and chloro(isopropyl)dimethylsilane. From reactions of acylchlorides RCOCl with 1 , diacyltellurides (RCO)₂Te (R = CH₃- 2 , i-C₃H₇- 3 , i-C₄H₉- 4 , (CH₃)₃CH₂-) 5 are isolated in pure state after removal of chloro(isopropyl)dimethylsilane. With succinic and glutaric dichlorides, 1 leads to impure cyclic diacyltellurides 6 (tellurosuccinic anhydride) and 7 (telluroglutaric anhydride). The reactions of bulky pivaloyl chloride and 1-adamantoyl chloride with 1 are too slow to be synthetically useful, but using bis(trimethylsilyl)telluride, dipivaloyltelluride 8 and di(1-adamantoyl)telluride 9 are straightforwardly available. 9 is accompanied by traces of 1-adamantanecarbonic anhydride 10 and by small amounts of di(1-adamantyl)ditelluride 11 . Constitutions of the new compounds 1 , 3–7 and 9 were confirmed by multinuclear NMR and mass spectroscopy. The structures of 9 and 10 were determined by X-ray crystallography.     

Synthesis and polycondensation of some new organotellurium compounds containing hydroxymethyl groups

A new series of organotellurium compounds [i.e. 2‐HOCH₂C₆H₄TeBr₃ (1), (2‐HOCH₂C₆H₄)₂TeBr₂ (2), (2‐HOCH₂C₆H₄)₂Te (3), (2‐HOCH₂C₆H₄Te? )₂ (4), 4‐HOCH₂C₆H₄TeBr₃ (5), (4‐HOCH₂C₆H₄)₂TeBr₂ (6), (4‐HOCH₂C₆H₄)₂Te (7), and (4‐HOCH₂C₆H₄Te? )₂ (8)] were prepared by reacting hydroxymethylphenylmercury chlorides with tellurium tetrabromide in dry dioxane. Bis(2‐hydroxymethylphenyl) telluride (3), bis(2‐hydroxymethylphenyl) ditelluride (4) and bis(4‐hydroxymethylphenyl) telluride (7) were polymerized by a solution polycondensation technique with toluene diisocyanate and terephthaloyl chloride, leading to new organic tellurium polyurethanes and polyesters. All the new compounds were characterized by elemental analysis and spectroscopic data. Copyright © 2002 John Wiley & Sons, Ltd.     

The mass spectral fragmentation of phenyl ω-dialkoxyethyl tellurides

The 70 eV mass spectrum of phenyl ω-dimethoxyethyl telluride [C₆H₅? Te? CH₂CH(OR)₂, R?CH₃]contains an intense peak at m/z 238 which corresponds to a rearrangement ion [C₆H₅? Te? OR]⁺. The formation of this species is further illustrated by the presence of a peak at m/z 241 in the spectrum of the hexadeuterated analog (R?CD₃) and a peak at m/z 252 in the spectrum of the ethyl analog (R?CH₂CH₃). These combined results illustrate the presence of only one of the alkoxyl groups in the rearrangement ion. Several other abundant ions that contain oxygen but not tellurium are present in the spectra of these compounds. High resolution analyses have aided in the determination of the origin and composition of several of the characteristic ions formed upon electron impact fragmentation of phenyl ω-dimethoxyethyl telluride.     

Synthese,Strukturen und Reaktivität von [(2,4,6-Ph3C6H2)Te(μ2-O)X]2 (X  Br und I)

Synthesis, Structures, and Reactivity of [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)X]₂ (X ? Br, I) [(2,4,6-Ph₃C₆H₂)Te]₂ reacts with iodine affording the aryltellurenic halide (2,4,6-Ph₃C₆H₂)TeI, which is oxidized by oxygen to yield [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)I]₂. It crystallizes with two molecules of dichloromethane in the monoclinic space group P2₁/c with a unit cell of the dimensions a = 911.3(4); b = 1153.3(2); c = 2244.1(9) pm; β = 93.53(2)°, Z = 2). The analogues bromo compound [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)Br]₂ is obtained by the reaction of [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)I]₂ with NH₄Br. It crystallizes with two molecules of xylene in the monoclinic space group P2₁/n (a = 1067.5(5); b = 1018.4(4); c = 2486.5(8) pm; β = 101.71(2)°; Z = 2). Both compounds are built up by two (2,4,6-Ph₃C₆H₂)TeX units (X ? Br, I) which are linked by two oxgen bridges to form centrosymmetric molecules. The Te? O? Te angles are 102°. Distinct Te? O bond lengths have been found (191.4(2) and 208.6(2) pm in [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)I]₂ and 189.8(4)/208.4(5 pm in the bromo compound).     

Molecular Structures of Dibromo[(E)2‐bromo‐2‐phenylvinyl]‐(phenyl) tellurium (IV) and Dibromo [(Z)‐2‐bromo‐2‐phenyl‐vinyl] (p‐tulyl) tellurium (IV) hydrate methanolate

The structures of title compounds, [TeBr₂(C₈H₆Br)(C₆H₅)] (I) and [TeBr₂(C₈H₆Br)(C₇H₉)](H₂O)(CT₃OH) (II), have been determined by X‐ray diffraction. The structures confirm that E‐ or Z‐type configuration of vinylic telluride depends on the polarity of solvent employed. In either structure, Te atom is in a trigonal dipyramide configuration with the lone pair of electrons in the equatorial position.     

New versatile organyltellurium(IV) halides: Synthesis and X-ray structural features of the telluronium tellurolate salts [PhTe(CH3)2]2[TeX6] (X = Cl, Br) and [Ph3Te][PhTeX4] (X = Cl, Br, I)

TeX₄ (X = Cl, Br) react in HCl/HBr with [Ph(CH₃)₂Te]X (X = Cl, Br) to give [PhTe(CH₃)₂]₂[TeCl₆] (1) and [PhTe(CH₃)₂]₂[TeBr₆] (2). The reaction of PhTeX₃ (X = Cl, Br, I) in cooled methanol with [(Ph)₃Te]X (X = Cl, Br, I) leads to [Ph₃Te][PhTeCl₄] (3), [Ph₃Te][PhTeBr₄] (4) and [Ph₃Te][PhTeI₄] (5). In the lattices of the telluronium tellurolate salts 1 and 2, octahedral TeCl₆ and TeBr₆ dianions are linked by telluronium cations through Te?Cl and Te?Br secondary bonds, attaining bidimensional (1) and three-dimensional (2) assemblies. The complexes 3, 4 and 5 show two kinds of Te?halogen secondary interactions: the anion-anion interactions, which form centrosymmetric dimers, and two identical sets of three telluronium-tellurolate interactions, which accomplish the centrosymmetric fundamental moiety of the supramolecular arrays of the three compounds, with the tellurium atoms attaining distorted octahedral geometries. Also phenyl C-H?halogen secondary interactions are structure forming forces in the crystalline structures of compounds 3, 4 and 5.     

The crystal structures of 1-allyl-1-bromo-3,4-benzo-1-telluracyclopentane [C8H8Te(C3H5)Br], 1-phenacyl-1-bromo-3,4-benzo-1-telluracyclopentane [C8H8Te(C8H7O)Br] and 1-deuteromethyl-1-iodo-3,4-benzo-1-telluracyclopentane [C8H8Te(CD3)I]; the trans effect in organotellurium bromides and iodides

The crystal structures of the title compounds have been determined from three-dimensional X-ray counter data.C₈H₈Te(CH₂CHCH₂)Br (I) is orthorhombic, space group Pbca with a 9.642(1), b 25.586(7), c 9.680(3) Å, Z = 8. The structure has been refined to R 5.2% for 1262 observed reflections.C₈H₈Te(CH₂COPh)Br (II) is orthorhombic, space group Pccn with a 23.593(6), b 14.337(3), c 9.180(2) Å, Z = 8. R = 5.5% for 1374 reflections.C₈H₈Te(CD₃)I (III) is orthorhombic, space group Pbca with a 11.200(3), b 15.976(2), c 23.328(3) Å, Z = 16. R = 5.6% for 2142 reflections.In I and II, tellurium is coordinated in an approximately octahedral geometry by the organic residues and three halogen contacts, with TeC and TeBr distances in the ranges 2.14(1)–2.19(1) Å and 3.328(2)–3.368(2) Å in (I) and 2.12(1)–2.18(1) Å and 3.292(2)–3.391(2) Å in II.In III, each of the two crystallographically independent complexes has tellurium coordinated in a distorted octahedral geometry. The TeC bond lengths are 2.10(2)–2.16(2) Å. In each case two TeI distances are in the range 3.596(2)–3.688(2) Å and a third, longer interaction (3.870(2) and 4.112(2) Å) completes the coordination.In each of the structures I–III the three covalent TeC bonds are oriented cis within the octahedra and exert a trans bond-lengthening effect on the Tehalogen interactions, precluding covalent-type bonding; the structures are essentially ionic, (C₈H₈TeR)⁺ cations and halide anions forming extended arrays.     

Untersuchungen zur plasmachemischen Darstellung von Trifluormethyl-Verbindungen der Elemente Quecksilber,Tellur und Xenon

Investigations on the Preparation of Trifluormethyl Compounds of the Elements Mercury, Tellurium, and Xenon (CF₃)₂Hg is formed from the reactions of C₂F₆ with Hg, HgX₂ (X = Cl, Br, I) or HgO in a chemical plasma. The best yields are obtained with Hg and HgO. The reaction of C₂F₆ with Te yields (CF₃)₂Te₂, which also can be identified in small amounts from the reactions of C₂F₆ with TeX₄ (X = Cl, Br). A similar reaction with Xe does not give any evidence for the formation of a noble gas compound.     

Organotellurium derivatives: III. Synthesis of anionic complexes of 1-telluracyclopentane(IV) 11 diiodide

Complexes containing tetrahalotelluracyclopenzane anions of the type (R₄M₂)⁺[C₄H₈TeX₂X′₂]^2- (where R = CH₃, C₂H₅, C₃H₇, C₄H₉, C₆H₁₃, C₇H₁₅ or C₆H₅; M = N, P, As or Sb; X = Cl, Br, or I and X′ = I, Cl, Br, NCO, NCS, or N₃) have been synthesized, (i) by the interaction of 1-telluracyclopentane $\text{1}\text{1}$ diiodide with the corresponding tetraorganoammonium, -phosphonium, -arsonium, or -stibonium halides in nonaqueous solvents and (ii) via halogen exchange between complex anions and silver or alkali metal halides. The second method also yielded several pseudohalide and mixed halide-pseudohalide derivatives. The ionic nature of the new complex anions has been established by conductance and molecular weight measurements. NMR and IR spectra of some of the derivatives are discussed.     

Synthesis,characterization and cytotoxicity of some triarylbismuth(V) di(N‐p‐toluenesulfonyl) aminoacetates and the crystal structure of (4‐CH3C6H4SO2NHCH2CO2)2Bi(C6H4Cl‐4)3

A series of triarylbismuth(V) di(N‐p‐toluenesulfonyl)aminoacetates with the formula (4‐CH₃C₆H₄SO₂NHCH₂CO₂)₂BiAr₃ (Ar?C₆H₅, 4‐CH₃C₆H₄, 4‐ClC₆H₄, 4‐BrC₆H₄) were synthesized and characterized by elemental analysis, IR, ¹H NMR and mass spectra. The crystal structure of (4‐CH₃C₆H₄SO₂NHCH₂CO₂)₂Bi(C₆H₄Cl‐4)₃ was determined and shows the bismuth to exist in a distorted trigonal bipyramidal geometry. Four human neoplastic cell lines (HL‐60, PC‐3MIE8, BGC‐823 and MDA‐MB‐435) were used to screen these compounds. The results indicate that these compounds at 10 μM show cytotoxicity. Copyright © 2004 John Wiley & Sons, Ltd.     

Darstellung und Kristallstrukturen von Dipyridiniomethan-Monohalogenohydro-closo-Dodecaboraten(2−), [(C5H5N)2CH2][B12H11X]; X = Cl,Br, I

Preparation and Crystal Structures of Dipyridiniomethane Monohalogenohydro-closo-Dodecaborates(2?), [(C₅H₅N)₂CH₂][B₁₂H₁₁X]; X = Cl, Br, I [B₁₂H₁₂]^2? reacts with dihalogenomethanes CH₂X₂ in presence of trifluoro acetic acid, yielding the monohalogenododecaborates [B₁₂H₁₁X]^2? (X = Cl, Br, I), which are separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound and higher halogenated products. The X-ray structure determinations of [(C₅H₅N)₂CH₂][B₁₂H₁₁Cl] · 2(CH₃)₂SO (orthorhombic, space group Pnma, a = 17.351(6), b = 16.034(5), c = 9.659(2) Å, Z = 4) and of the isotypic bromo and iodo compounds [(C₅H₅N)₂CH₂][B₁₂H₁₁X] (monoclinic, space group P2₁/n, Z = 4; for X = Br: a = 7.339(2), b = 15.275(3), c = 16.761(4) Å, β = 96.80(2)°; for X = I: a = 7.4436(8), b = 15.3510(8), c = 16.9213(16) Å, ß = 97.326(7)°) exhibit crystal lattices build up by columns of substituted boron clusters and angular dications [(C₅H₅N)₂CH₂]²⁺ orientated along the shortest axis which are assembled to alternating layers.     

Synthesis and properties of oligo(biradicals) composed of 1,3‐diphosphacyclobutane‐2,4‐diyl units and benzyl‐type linkers

We have succeeded in catenating two sterically encumbered 1,3‐di‐t‐butyl‐2,4‐bis(2,4,6‐tri‐t‐butylphenyl)‐1,3‐diphosphacyclobutane‐2,4‐diyl units with a spacer 1,2‐(CH₂)₂C₆H₄ to obtain bis(biradicals) as considerably stable compounds. We have discussed physicochemical properties of the dimer, together with DFT calculations of model compounds. Spectroscopic data, redox properties, and X‐ray structures of the oligo(biradicals) derivatives including other spacers like 1,3‐(CH₂)₂C₆H₄, 1,4‐(CH₂)₂C₆H₄, and 1,3,5‐(CH₂)₃C₆H₃, reveal that the P‐heterocyclic biradical moieties interact through nonconjugative pathways. These properties of oligo(biradicals) will facilitate to design novel molecular systems for electronics. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:404–411, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20625     

Perfluororganotellur-Verbindungen: Neue Untersuchungen zur Darstellung von Te(Rf)2 und CH3TeRf (Rf = C2F5, C3F7, C6F5)

Perfluoroorgano Tellurium Compounds: New Investigations on the Preparation of Te(R_f)₂ and CH₃TeR_f (R_f = C₂F₅, C₃F₇, C₆F₅) Methyl(perfluoroorgano) tellurium and bis(perfluoroorgano) tellurium compounds are synthesized in high yields from the photochemical or the thermal reactions of (CH₃)₂ Te with perfluoroorgano iodides in the presence of (C₂H₅)₃N. They are isolated in pure states. Another general method for the preparation of bis(perfluoroorgano) tellurium is the thermal reaction of TeCl₄ with bis(perfluoroorgano) mercury. The preparations and properties of the partially new compounds are described.     

Neue Synthesewege für Organohalogenstibane

New Methods for Synthesis of Organohalogenostibanes Organohalogenostibanes RSbX₂ (R = CH₃, C₆H₅; X = Cl, Br) and R₂SbX (R = C₆H₅; X = Cl) are received in good yields by alkylation or arylation of the corresponding antimony halides with Pb(CH₃)₄, Sn(CH₃)₄, Sb(CH₃)₃, or Sb(C₆H₅)₃. These methods are better than those, described in the literature for preparation of the compounds.     

Syntheses and Properties of Tetrakis(pentafluorophenyl)tellurium,Te(C6F5)4, and Related Compounds — Single Crystal Structures of Tris(pentafluorophenyl)tellurium Bromide,Te(C6F5)3Br,Tris(pentafluorophenyl)tellurium Trifluoromethanesulfonate, [Te(C6F5)3][OSO2CF3], and Bis(pentafluorophenyl)tellurium Oxide,Te(C6F5)2O

Te(C₆F₅)₄ was prepared from the reactions of TeCl₄ or Te(C₆F₅)₂Cl₂ with Grignard reagents or AgC₆F₅ in moderate to good yields. Substitution reactions with Me₃SiX (X = Cl, Br, OSO₂CF₃), with equimolar amounts of Br₂, with AgNO₃ and with H[BF₄] or BF₃·OEt₂ yielded the Te(C₆F₅)₃X derivatives (X = Cl, Br, OSO₂CF₃, NO₃, BF₄). Oxidation reactions of Cd, Hg, and Pd⁰ complexes led to Te(C₆F₅)₂ and the corresponding bis(pentafluorophenyl) derivatives M(C₆F₅)₂ (M = Cd, Hg, Pd) and with InBr to In(C₆F₅)₂Br. From very slow hydrolysis of Te(C₆F₅)₄ the oxide Te(C₆F₅)₂O was prepared. The thermal decomposition, the NMR and mass spectra of the partially new compounds are discussed. The crystal structures of Te(C₆F₅)₃Br (monoclinic, P2₁/a, Z = 4), [Te(C₆F₅)₃][OSO₂CF₃] (monoclinic, P2₁/n, Z = 16) and [Te(C₆F₅)₂O]₂ (triclinic, P1¯, Z = 2) were determined.     

Sulphur containing mesogens. The mesophasic behaviour of di(4-alkyloxybenzoates) of 4,4′-dimercaptobiphenyl

Abstract

A homologous series of di(4-alkyloxybenzoates) of 4,4′-dimercaptobiphenyl: CH₃(CH₂) _n-1O?C₆H₄?COS?C₆H₄?C₆H₄?SOC?C₆H₄?O(CH₂) _n-1CH₃,n=1–7, has been synthesized and the thermotropic liquid-crystalline behaviour investigated. All compounds exhibit enantiotropic mesomorphism over a remarkable temperature range. While the mesophase thermal stability is moderately higher than that found for the corresponding oxygenated analogues, the smectic stability is definitely lower. In fact, all the compounds are nematic but smectic mesomorphism (S_C) is observed for n = 7. Compounds with n = 6 or 7 exhibit enantiotropic highly ordered smectic (or disordered crystal) phases, probably S_G in type.     

C(sp)H?O and C(sp)H?O hydrogen bonds in acyclic- and cyclic-organotellurium carboxylates

The reactions between R₂TeI₂ (R₂=(CH₃)₂, C₄H₈, C₅H₁₀) and AgOCOR′ (R′=C₆H₅, 4-NO₂C₆H₄, CHCHC₆H₅) (molar ratio 1:2) yield diorganotellurium dicarboxylates: (CH₃)₂Te(OCOC₆H₅)₂ (1), C₅H₁₀ Te(OCOC₆H₅)₂ (2), C₄H₈Te(OCO4-NO₂C₆H₄)₂ (3) and C₄H₈Te(OCOCHCHC₆H₅)₂ (4). They are characterized by IR, (¹H, ¹³C, ¹²⁵Te) solution NMR; (¹³C, ¹²⁵Te) solid state NMR spectroscopy. The X-ray structures of 1-4 (the immediate environment about tellurium is that of distorted trigonal bipyramidal geometry with a stereochemically active electron lone pair) are described in the context of their ability to generate intermolecular CH?O hydrogen bonds, which lead to the formation of supramolecular assemblies.     

Arylsulphonamides of Amidothiophosphonic Acids

Abstract

Chemical structure-antimicrobian activity correlation in a thyophosphoric arysulphonamide class were estabilished^l. The aim of this paper is to present new compounds of same type: p-substituted arylsulphonylamides of amidothiophosphonic acids, I; N-methyl and S-methyl derivatives of them, II and respectively III, synthesyzed by schemes 1 and 2(R^?=_CC₈H₁₁, C₆H₅; NR₂=N(CH₃)₂, N(C₂H₅)2, N(C₂H₄)₂O; X=F, Cl, Br, H, CH₃, OCH₃).