Molecular and crystal structure of 1-bromo-1-butyl-3H-2,1-benzoxatellurole

The molecular and crystal structure of 1-bromo-1-butyl-3H-2,1-benzoxatellurole was determined by x-ray diffraction structural analysis. Without taking account of secondary interactions, the molecule contains a tetracoordinated tellurium atom with bisphenoidal bond configuration. The angle between the axial bromine and oxygen atoms is 172.1°. The intermolecular Te...Br contacts (3.592 Å) connect the individual dimers into planar dieters, which expands the coordination about the tellurium atom to octahedral.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 30, No. 3, pp. 417–419, March, 1994.     

Nitrogen-tellurium-containing heterocycles. 3. Reaction of 2-phenylbenzotellurazole at the heteroatoms

Reactions of 2-phenylbenzotellurazole at both heteroatoms are studied. -Telluranes and molecular complexes with mercury and palladium salts are prepared. Exchange of a tellurium atom by sulfur is achieved. Alkylation of a heteroatom of the pyrrole type, the tellurium atom, is achieved in a series of benzazoles for the first time.For Communication 2, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 989–993, July, 1989.     

THE CRYSTAL STRUCTURE OF 2-[(N,N-DIMETHYLAMINO)METHYL]BENZENETELLURENYL CHLORIDE

The crystal structure of 2-[N,N-dimethylamino)methyl]benzenetel-lurenyl chloride (2), a compound previously formulated as bis[[2-(N,N-dimethylamino)methyl]phenyl] ditelluride bis hydrochloride (1a), was determined. In the molecule 2, tellurium is bonded to the carbon of the phenyl group [2.120(3) Å], the nitrogen of the ortho dimethylamino substituent [2.362(3) Å], and the chlorine atom [2.536(1) Å]. There also is an intermolecular interaction of the tellurium atom with the phenyl ring of a neighbouring molecule [3.655(1) Å], resulting in the formation of zigzag chains along the b axis. The noncentrosymmetric space group of the crystal can be explained by the chiral surrounding of tellurium.     

Eigenschaften von Chalkogen-Chalkogen-Bindungen. XII. Reversible Tellurierung von Tetraisopropyldiphosphan; Stabilisierung von Tellurobis(diisopropylphosphan) als Tetracarbonylchromkomplex

Properties of Chalcogene-Chalcogene Bonds. XII. Reversible Telluration of Tetraisopropyldiphosphane, Stabilisation of Tellurobis(diisopropylphosphane) as Tetracarbonylchromium Complex Tetraisopropyldiphosphane 1 reacts with elemental tellurium by tellurium atom insertion to give tellurobis(diisopropylphosphane) 2. 2 is also available from sodium telluride with chlorodiisopropyl phosphane. ^lH, ^l3C, ^3lP and ^l25Te n.m.r. spectra confirm that in solution 2 is in an equilibrium with the educt 1 and elemental tellurium. Reaction of this equilibrium mixture with tetracarbonyl(norbornadiene)chromium(0) provides tetracarbonyl[tellurobis(diisopropylphosphane)]-chromium(0) 3. 3 was isolated in pure state as stable compound; different from 2,3 does not suffer from loss of tellurium at room temperature.     

New derivatives of 2-mercaptobenzotellurazole

New derivatives of 2-mercaptobenzotellurazole at the three reaction centers, the thiol group, nitrogen atom and tellurium atom, have been synthesized.     

Synthesis and Crystal Structures of Neutral Complexes of Tellurium(IV) – [PhTeX3L](X = Br,I; L = ethylenethiourea)

A three‐step one‐pot synthetic procedure to synthesize the neutral tellurium(IV) coordination compounds PhTeX₃L (X = Br, I and L = ethylenethiourea) has been developed and is described in this article. Oxidative halogenation of PhTeTePh in methanol generates the tellurium(II) derivative, PhTeX, which is subsequently complexed with ethylenethiourea, and, finally, further oxidative addition of additional halogen affords the corresponding tellurium(IV) compound PhTeX₃L in good yields. The final product was obtained by the slow evaporation of the reaction mixture as black crystals. The X‐ray structural analyses of the compounds show Te···X and X···X secondary interactions in the solid state and suggest a weak dependence of the formation of supramolecular assemblies on the nature of the halogen bonded to the tellurium atom.     

Theoretical study of selenium and tellurium impurities in (ZnO)6 clusters using DFT and TDDFT

Zinc oxide (ZnO) nanostructures have attracted much interest due to their potential applications in various fields including optoelectronics, glass industries, and solar cells. These compounds hold the promise of creating new materials that can advance energy technologies. In this work, a series of (ZnO)₆ clusters with selenium and tellurium applied as substitutional impurities has been studied. The investigated structures have been produced through the doping of (ZnO)₆ clusters by replacing an oxygen atom with a selenium or a tellurium atom at each time. The ground state geometric parameters of (ZnO)₆ structures, containing selenium or tellurium atoms as substitutional impurities, were calculated using density functional theory (DFT) with B3LYP and LanL2DZ basis set. Excited state energies and absorption wavelengths were computed using time‐dependent‐DFT (TDDFT). For the calculation of emission wavelengths, Hartree–Fock configuration interaction singles (HF/CIS) has been used in order to perform the excited state geometry optimization. This work led to some important results that can be helpful for developing novel THz sensitive materials and imaging detectors that may be an alternative to x‐rays detectors for radiology as well as for the development of solar cells and electroluminescent diodes. Zinc oxide (ZnO) nanostructures have attracted growing interest due to their potential applications in many technological fields, including optoelectronics, the glass industry, and energy. The presence of impurities, in particular selenium and tellurium, in ZnO‐based clusters can affect their structural and spectroscopic properties. Some of these doped nanostructures have favorable Terahertz emission characteristics that make them good candidates for applications in biology and medicine.     

Interaction of heterocyclic thioamides with tellurium(II) and tellurium(IV). Syntheses and crystal structures of bis[2-(2-thioxo-1,3- thiazolidin-3-yl)-4,5-dihydro-1,3- thiazolium]hexabromotellurate(IV) and tris(1- methylimidazole-2-(3H)-thione)tellurium(II) bromide

Reaction of 1,3-thiazolidine-2-thione with tellurium(IV) in hydrobromic acid medium gave the hexabromotellurate, [C₆H₉N₂S₃]₂²⁺[Te^IVBr₆]²⁻ (3). Reaction of 1-methylimidazoline-2-(3H)-thione (L″) with tellurium(IV), in hydrobromic acid medium, gave the mixed-ligand tellurium(II) complex [Te^IIL″₃Br]⁺Br⁻ (4). The structures of [C₆H₉N₂S₃]₂²⁺[Te^IVBr₆]²⁻ (3) and [Te^IIL″₃Br]⁺Br⁻ were determined by single crystal X-ray diffraction methods. In 3 the unit cell contains [TeBr₆]²⁻ anions and two [C₆H₉N₂S₃]⁺ cations. There is no direct bonding between the metal atom and the cations. In the anion only slight angular deviations from the perfect octahedral geometry are observed. The lone pair of electrons on tellurium(IV) is found to be stereochemically inert. In the cation the two five-membered heterocyclic rings adopt different conformations. In complex 4, in the solid state, the planar [Te^IIL″₃Br]⁺ cation and Br⁻ anion are held together by ionic interactions. In the cation, L″ is bonded to the central tellurium atom through the sulphur atom.     

Studies on 1,10-Phenanthroline Complexes of Some Hydroxyaryltellurium Trihalides

The synthesis and structural features of some newly synthesized 1,10-phenanthroline complexes of p-hydroxyphenyl-and 3-methyl-4-hydroxyphenyltellurium trihalides (chlorides, bromides, and iodides) are reported. The resulting complexes have been subjected to elemental analyses, conductance and cryoscopic measurements, infra-red and proton magnetic resonance spectral studies. Solution studies reveal the weak to 1:1 electrolyte type behavior of these complexes in solution. Spectral studies indicate the linkage of phenanthroline to the tellurium atom through the nitrogen atoms. Central tellurium atom in these complexes is hexa-coordinated in an octahedral way.     

Reaction of 1,1-dichloroethane with tellurium in the system hydrazine hydrate-potassium hydroxide

The reaction of 1,1-dichloroethane with tellurium in the system hydrazine hydrate-potassium hydroxide gave ethyltellanyl derivatives as a result of replacement of one chlorine atom in the substrate by tellurium, and of the other, by hydrogen. Probable mechanisms of reduction of the C-Cl bond and mass spectra of the products were considered. The mass spectra of ditelluroacetals revealed unusual rearrangement of the molecular ion, leading to the formation of Te-Te and new C-C bond.     

Reaction of tellurium with dichloromethane in the system hydrazine hydrate-alkali

Tellurium reacts with dichloromethane in the system hydrazine hydrate-alkali substituting one chlorine atom by tellurium whereas the second chlorine atom undergoes reductive substitution by hydrogen leading to the formation of methyltellanyl derivatives. Tentative mechanism of reduction is discussed. The discovered reaction allows the preparation of organotellurium compounds containing the MeTe group, including those involving other chalcogens.     

Low-temperature 1H, 13C, 77Se,and 125Te NMR studies on the apical-apical ligand exchange via the hypervalent tellurium and selenium ate complexes [10-M-3(C3); M = Se,Te] in the reactions of diaryl tellurides and selenides with aryllithium reagents

Pentafluorophenyl phenyl telluride ( 1 ) and 3,5-dichloro-2,4,6-trifluorophenyl phenyl telluride ( 2 ) react with pentafluorophenyllithium or 3,5-dichloro-2,4,6-trifluorophenyllithium in THF at low temperatures to form the corresponding tellurium ate complexes ( A ) and ( B ) as sole intermediates in the ligand exchange on the hypervalent tellurium atom. The corresponding selenides ( 3 ) and ( 4 ) also react with identical aryllithium reagents in THF to form the discrete intermediates, selenium ate complexes ( C ) and ( D ), in the exchange reactions. In these ligand exchange reactions of tellurides and selenides, electron-withdrawing ligands occupy the apical positions and the exchange takes place between these apical-oriented groups. The low-temperature ¹H, ¹³C, ⁷⁷Se, and ¹²⁵Te NMR spectroscopic techniques are effective methods for detection of unstable tellurium and selenium ate complexes.     

Synthesis of enantiomerically pure telluronium salts by the reaction of chiral tellurides with alkyl halides

Enantiomerically pure benzyl and ethoxycarbonylmethyl telluronium salts 4, using 2-exo-hydroxy-10-bornyl group as a chiral ligand, have been prepared in good yield and diastereoselectivity by the reaction of chiral tellurides 3 with alkyl halides. A structure with R_Te absolute configuration at the tellurium atom was confirmed by an X-ray analysis of 4a.     

Gravimetric analysis of high purity tellurium for purity evaluation

Gravimetric analysis was utilized for purity evaluation of high purity tellurium, which was a raw material of a tellurium standard solution. Using a method in which tellurium was precipitated as elemental tellurium with hydrazinium after dissolution of the high purity tellurium, an avoidable positive error (ca. 0.02%) was observed. It seems that a cause of the positive error is oxidation of the tellurium or occlusion of the solvent during the precipitation. On the other hand, when the precipitated elemental tellurium was further converted into tellurium oxide by heating at 600 °C, the positive error disappeared. Finally, the purity of the starting tellurium was evaluated from the recovery of tellurium oxide with sufficient accuracy for a raw material of a tellurium standard solution (0.017% expanded uncertainty (k = 2)).     

First synthesis and structural determination of 1, 1′-spirobis(3H-2, 1-benzoxatellurole)-3, 3′-dione ([10-Te-4(C202)])

1, 1′-Spirobis(3H-2, 1-benzoxatellurole) -3, 3′-dione [10-Te-4(C202)] ( 1c ) with five-membered spirorings was prepared, and its molecular structure was determined by X-ray crystallographic analysis. The two types of arrangement of the ligands about the central tellurium atom show considerably distorted trigonal bipyramidal (TBP) geometries. The tellurane 1c undergoes a ring-opening reaction on treatment with aqueous sodium hydroxide to afford the telluroxide 10 , which reacts with aqueous hydrochloric acid at room temperature to give again the tellurane 1c in quantitative yield. © 1995 John Wiley & Sons, Inc.     

Mehrfachbindungen zwischen Hauptgruppenelementen und Übergangsmetallen: XLVVI. Nachweis der Elektrophilie eines trigonal-planar koordinierten Telluratoms

The central tellurium atom coordinated to three manganese atoms in the compound (υ₃-Te)[(η⁵-C₅H₅)Mn(CO)₂]₃ (1) exhibits electrophilic reactivity, thus undergoing methylation with methyllithium to yield the anion [(μ₃-TeCH₃){;(η⁵-C₅H₅)Mn(CO)₂};₃]⁻, whose structure was determined crystallographically. While the precursor compound 1 contains a planar Mn₃Te core structure (d(Mn-Te) 248.7 pm, av.), carbanion addition effects pyramidalization of this fragment (d(Mn-Te) 257.7 pm, av.), with the tellurium atom appearing at a distance of 56 pm above the plane defined by the three manganese atoms.     

Toward modeling phosphate tellurate glasses: the devitrification and addition of gadolinium ions behavior

Glasses in the xGd2O3 x (100 - x)[7TeO2 x 3P2O5] system with 0 < or = x < or = 20 mol % have been prepared using the melt quenching method. The influence of gadolinium ions on structural behavior of the phosphate tellurate glass has been investigated using infrared spectroscopy and density functional theory (DFT) calculations. The addition of gadolinium ions into the host glass matrix leads to an increase of the glass network polymerization due to the replacement of P-O-P bonds by the more resistant P-O-Te bonds having as result the improvement of the chemical durability of the glass. The structural evolution of the studied glasses with the gradual increase of the gadolinium oxide content up to 20 mol % could be explained by considering that the excess of oxygen may be accommodated by the conversion of some orthophosphate structural units into metaphosphate or/and pyrophosphate units. X-ray diffraction and IR spectra revealed that heat treatment of the samples also causes an increase of the glass network polymerization for heat treatment times, t, up to 36 h, while for 36 h > t > or = 48 h showed a drastic structural modification which lead to the apparition of the Te4P2O13 crystalline phase. DFT calculations show that tellurium atoms occupy two different sites in the proposed model. In the first case the tellurium atom is coordinated with four oxygen atoms giving a trigonal bipyramide arrangement, while in the second case the tellurium atom is coordinated with three O atoms. The calculated IR absorption spectrum of the proposed model for phosphotellurite glasses is in good agreement with the experimental absorption data.     

Long-range relativistic heavy atom effect on 1H NMR chemical shifts of selenium- and tellurium-containing compounds

Previously unknown manifestation of heavy atom effect on the NMR chemical shifts of β- and γ-protons initiated by the relativistic effects of the tellurium and selenium atoms has been investigated in the representative series of selenium- and tellurium-containing compounds. To approve the four-component density functional approach to be the appropriate tool for the investigation of the heavy atom on light atom effect (HALA), the benchmark calculations of the proton chemical shifts have been performed at the CCSD level using comprehensively chosen locally dense basis set with taking into account solvent, vibrational, and relativistic corrections. A good agreement with the experimental data was achieved. The magnitudes of the relativistic HALA corrections to β- and γ-proton chemical shifts were found to vary in a wide range, namely from −3.08 ppm for the γ-proton of methyltelluraldehyde to 14.51 ppm for β-proton in benzotelluraldehyde.     

Verfeinerung der Kristallstruktur von Te2O3(SO4)

The crystal structure of ditellurium(IV)-trioxide sulfate, Te₂O₃(SO₄)—space group Pmn2₁–C _2v ⁷ ;a=8.879 (2),b=6.936 (2),c=4.646 (4) Å,Z=2—has been determined and refined by least-squares, using three-dimensionalX-ray data (1188 independent reflexions) to a final R-value of 6.3%.The crystal structure comprises puckered tellurium(IV)—oxygen layers in which the tellurium atoms are linked together by three oxygen bridges (Te–O 1.907, 1.945, 2.011 Å). The SO₄ groups are arranged between these layers. Two oxygen atoms of each SO₄ group are bonded to two adjacent tellurium atoms of one layer [Te–O(S) 2.270 Å] and the tellurium atoms show a (3+1) coordination. A third oxygen atom of the SO₄ group is in weak interaction with two adjacent tellurium atoms of the same layer (Te–O 2.603 Å) whereas the fourth oxygen atom has distances of 2.866 Å to two adjacent tellurium atoms of the next layer and effects a very weak interaction between the

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Herrn Prof. Dr.R. Kieffer zu seinem 70. Geburtstag gewidmet.     

Atomistic band gap engineering in donor-acceptor polymers

We have synthesized a series of cyclopentadithiophene-benzochalcogenodiazole donor-acceptor (D-A) copolymers, wherein a single atom in the benzochalcogenodiazole unit is varied from sulfur to selenium to tellurium, which allows us to explicitly study sulfur to selenium to tellurium substitution in D-A copolymers for the first time. The synthesis of S- and Se-containing polymers is straightforward; however, Te-containing polymers must be prepared by postpolymerization single atom substitution. All of the polymers have the representative dual-band optical absorption profile, consisting of both a low- and high-energy optical transition. Optical spectroscopy reveals that heavy atom substitution leads to a red-shift in the low-energy transition, while the high-energy band remains relatively constant in energy. The red-shift in the low-energy transition leads to optical band gap values of 1.59, 1.46, and 1.06 eV for the S-, Se-, and Te-containing polymers, respectively. Additionally, the strength of the low-energy band decreases, while the high-energy band remains constant. These trends cannot be explained by the present D and A theory where optical properties are governed exclusively by the strength of D and A units. A series of optical spectroscopy experiments, solvatochromism studies, density functional theory (DFT) calculations, and time-dependent DFT calculations are used to understand these trends. The red-shift in low-energy absorption is likely due to both a decrease in ionization potential and an increase in bond length and decrease in acceptor aromaticity. The loss of intensity of the low-energy band is likely the result of a loss of electronegativity and the acceptor unit's ability to separate charge. Overall, in addition to the established theory that difference in electron density of the D and A units controls the band gap, single atom substitution at key positions can be used to control the band gap of D-A copolymers.