Voltammetric Ultra Trace Determination of Tellurium

Abstract

A simple and convenient method is described for the determination of low concentration tellurium based on differential pulse polarographic reduction of Te(IV) in alkaline medium. Linearity of the calibration curve was achieved up to 25.5 ppm with a limit of determination of 0.02 µg/mL. The possible interference of coexisting metal ions was examined and ruled out. The method has been successfully applied for the analysis of tellurium in industrial waste samples.     

Determination of Tellurium by Instrumental Photon Activation Analysis

Abstract

Tellurium has been determined at milligram and submilligram levels in the presence of uranium by a strictly instrumental photon activation ¹²¹ analysis procedure. The 575 keV gamma ray of Te was measured. At a decay time of three weeks, this gamma ray peak was interference-free. As little as 0.4 mg of tellurium was determined and the method evidences that sensitivity would increase with irradiation time.     

Coordination Patterns of the Diphenyl-Phosphinodithioato Ligand in Tellurium Compounds

Abstract.

Solid state monomeric structures with monometallic biconnective (bidentate) diphenylphosphinodithioato groups were found in Ph₂Te(S₂PPh₂)₂ (1) or [Ph₃Te][S₂PPh₂] (2), while in the polymeric associations [Te₂(S₂PPh₂)₂]_n (3) and [PhTeS(S)PPh₂]_n (4) bimetallic biconnective (bridging) and monodentate biconnective (bridging) patterns were established by X-ray diffractometry. [Te(S₂PPh₂)₃]₂ (5) exhibits an unusual dimeric structure, with both monometallic biconnective and bimetallic triconnective ligand units.     

Recent Studies of Multiply Bonded Selenium and Tellurium Compounds

Abstract

Several aspects of recent developments in the chemistry of multiply bonded selenium and tellurium compounds are surveyed in this article. These include (a) tellurium(IV)-nitrogen compounds, (b) complexes with two (or more) terminal Group 14–Group 16 linkages, and (c) a new approach to previously inaccessible ligands containing Group 15–Group 16 functionalities.     

The Reactions of Sulfur,Selenium and Tellurium with Fluorosulfuric Acid

Abstract

In fluorosulfuric acid, four different sulfur species: S₂ ⁺., S⁺., S(II+), S(IV+), 3 different selenium species: Se₂ ⁺., Se(II+), Se(IV+), and 3 different Tellurium species: Te₂ ²⁺, Te(II+) and Te(IV+) have been observed spectrophotometrically and electrochemically by varying the composition of the solvent from basic (non-oxidizing) medium (0.1M solution of NaSO₃F) to oxidizing media (0.5M solution of SO₃).     

Developments on the Chemistry of Tellurium and Selenium Azides

Abstract

We have been carrying out systematic studies on the preparation and properties of tellurium halide and pseudohalide compounds with a focus on tellurium azides. We were successful in the synthesis of various tellurium azides of both covalent and ionic nature. Several tellurium(IV) azides, tellurium(II) azides, and the first tellurium(VI) azides can be prepared in reasonable amounts. The first structural information of selenium azides is obtained for covalent and ionic derivatives, and spectroscopic data for the existence of selenium(iv) polyazides.     

Synthesis and Stereochemistry of Optically Active Selenium and Tellurium Compounds

Abstract

The synthesis and stereochemistry of tricoordinated optically active selenium and tellurium compounds are described. Telluronium salts, telluronium imides, and seleninic acids were prepared and optically resolved by fractional recrystallization of diastereomeric mixtures or by chromatography using a chiral column of racemic mixtures. Diphenyl dichalcogenides also were optically resolved by chiral crystallization. Their absolute configurations were determined or estimated based on X-ray crystallographic analysis, specific rotations, and circular dichroism spectra. The kinetic studies and the mechanism for the racemization were also studied.     

The Nature of the Phosphorus Tellurium Bond in Tellurophosphoranes and their Derivatives

Abstract

Tellurophosphoranes, which may be considered as phosphane chalkogenides (I) or as phosphane stabilized tellurium atoms (II), form coordination compounds III and IV. The nature of both the phosphorus tellurium and the phosphorus element bond is discussed from chemical and spectroscopic properties.     

Diaryl Tellurium Dihalides: From Te-Tetracoordinated Compounds to Te-Tricoordinated Molecular Complexes

Abstract

X-ray structural studies demonstrate that diaryl tellurium diiodides can be constrained by steric factors (ortho-alkyl substituents) to adopt a trigonal pyramidal structure in preference to the expected bisphenoidal structure. DFT calculations are shown to reproduce successfully structural details of the title compounds; they allow one to predict which coordination number should be energetically favored. All compounds are chiral, but the barrier to stereomutation by intra- and intermolecular pathways (60–85 kJmol^?1) is rather low.     

Synthesis of Imidazolato and 2-Methyl-Imidazolato Derivatives of Tellurium(IV)

INTRODUCTION

The chemistry of S-N compounds has been well established^[1] in the past few years and the stability was accounted in terms of extensive π bonding^[2,3]. The diversity of these compounds tempted chemsits to explore analogous Se-N and Te-N compounds. However, the poor or even absence of π bonding with heavier Se and Te posed problem to synthesize such compounds in the past. The chemistry of Se-N and Te-N compounds has been developed extensively by introducing new synthetic precursors^[4] in the last decade or so. We have observed that N-trimethyl silylimidazole and 2-methyl silylimidazole are potential reagents for peperation of monomeric transition metal imidazolates and Tin(IV) imidazolate^[5,6]. We, therefore, thought worthwhile to synthesize amido derivatives of Te(IV) incorporating these π delocalised heterocycles which acts as potential 4e (both σ and π) donors.     

The Determination of Trace Amounts of Tellurium and Selenium in Gallium Metal

Abstract

Analytical methods have been developed for the separation, concentration and determination of trace quantities of tellurium and selenium from primary and scrap gallium metal. A chloroform extraction is made of the tellurium diethyldithiocarbamate complex at a pH of 8.5. This extraction, in the presence of ammonium citrate, allows the satisfactory determination of tellurium by emission or atomic absorption spectrohcopy. The limit of sensitivity of the method is 0.5 pg of tellurium in 1.0 gram of gallium (0.5 ppm Te).     

Tetravalent Tellurium Ligands

Oxidative addition of TeCl₄ to Vaska's complex gave the trichlorotelluronium complex [IrCl₂(TeCl₃)(CO)(PPh₃)₂] (structure depicted), which contains a rare example of a structurally characterized tetravalent tellurium ligand. The coordination at the Te^IV center is—in full agreement with the VSEPR model—distorted trigonal bipyramidal.     

Antibacterial Activities of Tellurium Nanomaterials

We prepared four differently shaped Te nanomaterials (NMs) as antibacterial reagents against Escherichia coli. By controlling the concentrations of hydrazine (N₂H₄) as reducing agent, NaCl, and temperature, we prepared Te nanowires, nanopencils, nanorices, and nanocubes. These four Te NMs resulted in a live/dead ratio of E. coli cells of less than 0.1, which is smaller than that of Ag nanoparticles. The order of antibacterial activity against E. coli is nanocubes ≈ nanorices > nanopencils ≈ nanowires. This is in good agreement with the concentration order of tellurite (TeO₃²⁻) ions released from Te NMs in E. coli cells, revealing that TeO₃²⁻ ions account for the antibacterial activity of the four Te NMs. We found that spherical Te nanoparticles (32 nm in diameter) with TeO₃²⁻ ions were formed in the E. coli cells. Compared to Ag nanoparticles that are commonly used as antibacterial reagents, Te NMs have higher antibacterial activity and lower toxicity. Thus, Te NMs hold great practical potential as a new and efficient antibacterial agent.     

Synthesis of CdTe Quantum Dots with Tunable Photoluminescence Using Tellurium Dioxide as Tellurium Source

A simple and convenient method has been developed for synthesis of water‐soluble CdTe quantum dots (QDs) under ambient atmospheric conditions. In contrast to the traditional aqueous synthesis, green to red emitting CdTe QDs were prepared by using TeO₂ to replace Te or Al₂Te₃ as tellurium source in this method. The influences of experimental variables, including pH value, 3‐mercaptopropionic acid (MPA)/Cd and Te/Cd molar ratios, on the emission peak and photoluminescence (PL) quantum yield (QY) of the obtained CdTe QDs have been systematically investigated. Experimental results indicate that green to red emitting CdTe QDs with a maximum photoluminescence quantum yield of 35.4% can be prepared at pH 11.3 and n_(Cd):n_(Te):n_(MPA)=1:0.1:1.7.     

Determination of Tellurium by Gas Phase Molecular Absorption Spectrometry After Hydrogen Telluride Generation

Abstract

A method for determination of tellurium(IV) or tellurium(VI) is described that involves hydrogen telluride generation by reduction with sodium tetrahydro-borate(III), evolution of hydride with HCl solution, transport into a flow-cell placed in a UV-visible molecular absorption spectrophotometer and measurement of gas at 190 nm. Hydride generation and determination procedures are optimized, based on height and area of absorbance versus time profile of hydrogen telluride generated. Using the best experimental conditions found the calibration curve is linear from 5 to 100 μg/ml of tellurium, 1.1 μg/ml of tellurium(IV) or 3.1 μg/ml of tellurium(VI) can be detected, and relative standard deviation ranges from 4 to 7%. The method is applied to the analysis of additives for synthetic rubber making.     

Cathodic Stripping Voltammetric Determination of Tellurium(IV) with in situ Plated Bismuth-Film Electrode

Abstract

A very sensitive and reliable method is proposed for the determination of tellurium(IV) [Te(IV)] by Osteryoung square-wave cathodic stripping voltammetry. This method is based on the reduction of Te(IV) with bismuth(III) onto an edge-plane pyrolytic graphite electrode, followed by a cathodic potential scan. The reduced Te gave a well-defined catalytic hydrogen wave at ?1200 mV vs. Ag/AgCl. The peak height of the catalytic wave was directly proportional to the initial Te(IV) concentration in the concentration ranges of 0.01–0.10 and 0.1–1.0 µg L^?1 with 30 s deposition time. A 3σ detection limit of 1.0 ng L^?1 Te(IV) was obtained with the same deposition time. The relative standard deviation was 3% on replicate runs (n = 5) for the determination of 0.1 µg L^?1 Te(IV). Analytical results of natural water samples demonstrate that the proposed method is applicable to the determination of traces of Te(IV).     

Peroxide Coordination of Tellurium in Aqueous Solutions

Tellurium–peroxo complexes in aqueous solutions have never been reported. In this work, ammonium peroxotellurates (NH₄)₄Te₂(μ‐OO)₂(μ‐O)O₄(OH)₂ ( 1 ) and (NH₄)₅Te₂(μ‐OO)₂(μ‐O)O₅(OH)?1.28 H₂O?0.72 H₂O₂ ( 2 ) were isolated from 5 % hydrogen peroxide aqueous solutions of ammonium tellurate and characterized by single‐crystal and powder X‐ray diffraction analysis, by Raman spectroscopy and thermal analysis. The crystal structure of 1 comprises ammonium cations and a symmetric binuclear peroxotellurate anion [Te₂(μ‐OO)₂(μ‐O)O₄(OH)₂]^4?. The structure of 2 consists of an unsymmetrical [Te₂(μ‐OO)₂(μ‐O)O₅(OH)]^5? anion, ammonium cations, hydrogen peroxide, and water. Peroxotellurate anions in both 1 and 2 contain a binuclear Te₂(μ‐OO)₂(μ‐O) fragment with one μ‐oxo‐ and two μ‐peroxo bridging groups. ¹²⁵Te NMR spectroscopic analysis shows that the peroxo bridged bitellurate anions are the dominant species in solution, with 3–40 %wt H₂O₂ and for pH values above 9. DFT calculations of the peroxotellurate anion confirm its higher thermodynamic stability compared with those of the oxotellurate analogues. This is the first direct evidence for tellurium–peroxide coordination in any aqueous system and the first report of inorganic tellurium–peroxo complexes. General features common to all reported p‐block element peroxides could be discerned by the characterization of aqueous and crystalline peroxotellurates.     

Tellurium Chloride Complexes in Nonaqueous Solutions

Tellurium(IV) complexes (R₄N)₂[TeCl₆] (T6), (R₄N)[TeCl₅] (T5), and (R₄N)[TeCl₄OH] (T4), where (R₄N)⁺ is tetrabutyl, tetraoctyl, and trialkyl benzyl ammonium cations, were synthesized. Tellurium distribution between aqueous HCl solutions and trialkyl benzyl ammonium chloride solution in caprylic acid was studied. The ¹²⁵Te NMR spectra of aqueous HCl solutions of tellurium have a single averaged peak, whose chemical shift (CS) depends on the acid concentration. ¹²⁵Te NMR spectroscopy has shown that the T4 complex in nonaqueous solutions is kinetically inert and the ligand exchange with the T6 and T5 complexes is retarded. In contrast, the T5 and T6 complexes, when simultaneously present in nonaqueous solutions, rapidly exchange ligands. ¹²⁵Te NMR, IR, Raman, and UV spectroscopic studies have shown that under standard conditions, the reaction (Bu₄N)[TeCl₅]+Bu₄NCl = (Bu₄N)₂[TeCl₆] G⁰ = -19.1(1 ± 0.3) kJ/mol and H⁰ = -6.5(1 ± 0.2) kJ/mol) takes place in methylene chloride solution. The symmetry groups of the synthesized complexes in the solid state and CSs for tellurium solutions (0.2 gatom/liter Te) in methylene chloride were determined: O_h and –58 ppm for T6; C_4v and +75 ppm for T5; and C_3v and +54 ppm for T4 (CS = 0 for a 0.2 mol/liter TeO₂ solution in 11.4 mol/liter HCl).     

Chalcogen Chiral Ylides for the Catalytic Asymmetric Epoxidation of Aldehydes: From Sulfur to Selenium and Tellurium

Abstract

The reaction of novel chiral selenonium and telluronium ylides was investigated with aldehydes and compared to the sulfur analogues. (2R,5R)-2,5-Dimethylselenolane was prepared and reacted as a catalyst for the benzylidenation of aldehydes. Disubstituted epoxides were readily prepared with a (surprising) absence of diastereoselectivity, and with enantiomeric excesses higher than 90%. The reaction of a tellurium analogue, (2S,5S)-2,5-diethyltellurolane, afforded the oxirane in very moderate yield and e.e.'s in the range of 62–82%. Though this was less productive, it is the first report of a chiral telluronium ylide leading to an asymmetric epoxidation of aldehydes.     

Ethoxytelluration of Terminal Alkenes with Tellurium Tetrahalides

Efficient methods for the preparation of trichloro- and tribromo(2-ethoxyalkyl)-λ⁴-tellanes in 80 to 100% yield have been developed on the basis of ethoxytelluration of hex-1-ene, hept-1-ene, and oct-1-ene with tellurium tetrahalides. Tribromo(2-ethoxyalkyl)-λ⁴-tellanes have been reduced to 1,2-bis(2-ethoxyalkyl)ditellanes in 92–95% yield with the system NaBH₄–H₂O–THF.