Reaction of thallium(III) salts with homoallylic alcohols: ring contraction vs. dimethoxylation

The oxidation of 2-(3,4-dihydronaphthalen-1-yl)-ethanol (1) with a variety of thallium(III) salts was investigated. An indan, formed by a ring contraction reaction, was obtained in good to moderate yields under a variety of reaction conditions: i) thallium triacetate (TTA) in aqueous AcOH; ii) thallium tris-trifluoroacetate (TTFA) in aqueous TFA; iii) TTFA in CH(2)Cl(2); iv) thallium tripropionate (TTP) in aqueous propionic acid and v) thallium tris-[(S)-(-)-triacetoxypropionate] in aqueous (S)-(-)-2-acetoxypropionic acid. On the other hand, the reaction of compound 1 with TTA in methanol led to a 2:1 mixture of the corresponding cis- and trans-dimethoxylated compounds, respectively.These compounds were formed by a thallium-promoted addition of methanol to the double bond.     

Chloride, -Hydride and -Borohydride Derivatives of Difluorenyl Thallium(III)

Chloride¹), borohydrides²) and hydrides³) of dicyclopentadienyl thallium (III) and diindenyl thallium (III) have already been reported. The present communication deals with a study on the preparation and characterization of difluorenyl thallium (III) chloride, -hydride and -borohydride.     

Anhydrous thallium hydrogen L-glutamate: polymer networks formed by sandwich layers of oxygen-coordinated thallium ions cores shielded by hydrogen L-glutamate counterions

Anhydrous thallium hydrogen L-glutamate [Tl(L-GluH)] crystallizes from water (space group P2(1)) with a layer structure in which the thallium ions are penta- and hexacoordinated exclusively by the oxygen atoms of the γ-carboxylate group of the hydrogen L-glutamate anions to form a two-dimensional coordination polymer. The thallium-oxygen layer is composed of Tl(2)O(2) and TlCO(2) quadrangles and is only 3 ? high. Only one hemisphere of the thallium ions participates in coordination, indicative of the presence of the 6s(2) lone pair of electrons. The thallium-oxygen assemblies are shielded by the hydrogen l-glutamate anions. Only the carbon atom of the α-carboxylate group deviates from the plane spanned by the thallium ions, the γ-carboxylate groups and the proton bearing carbon atoms, which are in trans conformation. Given the abundance of L-glutamic and L-aspartic acid in biological systems on the one hand and the high toxicity of thallium on the other hand, it is worth mentioning that the dominant structural motifs in the crystal structure of [Tl(L-GluH)] strongly resemble their corresponding analogues in the crystalline phase of [K(L-AspH)(H(2)O)(2)].     

Kinetics of the oxidation of cyclohexene by thallium(III) acetate

The kinetics of the reaction by which thallium(III) acetate oxidizes cyclohexene in glacial acetic acid medium, has been studied by UV spectrophotometric observation at 30°C. The consumption of thallium(III) acetate follows a second-order rate law exhibiting first-order dependence on each of thallium(III) acetate and cyclohexene; however, the first-order dependence on cyclohexene disappears at high cyclohexene concentrations as pseudo-first-order conditions prevail above 0.2 M cyclohexene. A steady-state model of the following form is proposed: where Tl, Cy, and Com are units of Thallium(III) acetate, cyclohexene, and a reaction complex. The value of k₂ has been evaluated as 0.00027 and (k_?1 + k₂) as 0.0385k₁. For low thallium(III) acetate concentrations the reaction kinetics follow the rate law: where α = the excess concentration of cyclohexene over thallium(III) triacetate. For thallium(III) acetate concentrations above 0.02 M, double salt formation of thallium(III) acetate with product thallium(I) acetate removes thallium(III) acetate from the reaction and a modified rate law is observed. Runge–Kutta numerical solutions to the differential equations provide confirmation that the rate expressions are valid in predicting the observed concentrations of thallium(III) acetate.     

Some studies on thallium oxalates. VI

The effect of the thallium(I) concentration on the potentiometric titration of thallium(III) with oxalic acid in 0.1M HNO₃ or 0.05M H₂SO₄ is studied, and conditions are established for the preparation of the thallium(I) bis-oxalato diaquo thallate(III) complex. Chemical analysis of the salt corresponds to the formula T1^I(T1^III(C₂O₄)₂) · 5 H₂O. Thermal decomposition studies on the complex using TG, DTG and DTA techniques indicate the formation of thallium(I) oxalate (stable from 130° to 320°) as the intermediate, the final product being a mixture of thallium(I) oxide and thallium(III) oxide (stable from 520° to 600°). Infrared absorption spectra, X-ray diffraction patterns and microscopic observations are used to characterise the complex and the intermediate.     

Radiation induced exchange reaction between thallium(I) and thallium(III)—Comparison of sulfuric acid and perchiloric acid solution

The rate constant of radiation induced exchange reaction between thallium(I) and thallium(III) ions has been studied for elucidating the mechanisms which are responsible for (T1(II) intermediates or bridging groups (SO ₄ ^2– ) in sulfuric acid and perchloric acid solutions. It was found that the radiation induced exchange reaction is accelerated by the sulfate ion, and the rate of the thallium(II)-thallium(I) reaction is faster than that of the thallium(II)-thallium(III) process in perchloric acid solution.     

A simple and rapid spectrophotometric determination of thallium(III) with trifluoperazine hydrochloride.

A simple, sensitive and rapid spectrophotometric method was developed for the determination of thallium(III) using trifluoperazine hydrochloride (TFPH). The method is based on the oxidation of TFPH by thallium(III) in a phosphoric acid medium to form a red-colored radical cation with an absorption maximum at 505 nm. Beer's law is valid over the concentration range of 0.5 - 6.5 microg ml(-1) of thallium(III). The molar absorptivity and Sandell's sensitivity of the color system are 2.14 x 10(4) l mol(-1) cm(-1) and 0.0095 microg cm(-2), respectively. The optimum reaction conditions and other analytical parameters were evaluated. The tolerance limit of the method towards various ions usually associated with thallium has been studied. The proposed method has been successfully applied to the analysis of thallium in alloys, minerals, standard reference material, water, and urine samples.     

Studies with dithizone : Part 26. The interaction of thallium(III) with solutions of dithizone in organic solvents

The strong oxidising capacity of thallium(III) dominates its reaction with solutions of dithizone (H₂Dz) in organic solvents. When carbon tetrachloride is used as solvent, the unstable thallium(III) complex Tl(HDz)³ is found in the organic phase but it very quickly disproportionates to the thallium(I) complex [Tl(HDz)], and bis-1,5-diphenylformazan-3-yl-disulphide. This reaction is notably faster in chloroform, in which thallium(I) dithizonate is the first identifiable product. In contact with an acidic aqueous phase, thallium(I) dithizonate is reverted to regenerate dithizone in the organic phase and Tl⁺ ions appear in the aqueous phase. Organic solutions of the disulphide disproportionate spontaneously by first-order kinetics to give an equimolar mixture of dithizone and the mesoionic compound, 2,3-diphenyl-2,3-dihydrotetrazolium-5-thiolate: this change is much slower in carbon tetrachloride than in the more polar chloroform and is catalysed by both Tl⁺ and Tl³⁺. If thallium(III) is present in excess, the mesoionic compound is the principal oxidation product of the dithizone although a dication may also be formed. The mesoionic compound does not react with thallium(I) but forms a water-soluble 2:1 complex with thallium(III); partition of this complex into the organic phase is uninfluenced by chloride ions. Because of the large number of competing reactions, the composition of the reaction mixture at any stage of the reaction between thallium(III) and dithizone depends on the relative concentrations of the components, the order in which they are brought together, the time elapsed after mixing, the pH of the aqueous phase, and the nature of the organic solvent.     

Conformational studies of dicyclohexylthallium chloride,bis(4-methylcyclohexyl)thallium chloride and bis(4-tert-butylcyclohexyl)thallium chloride by 1H NMR

Vicinal thallium–hydrogen coupling constants are used to discuss conformations in dicyclohexylthallium chloride, bis(4-methylcyclohexyl)thallium chloride and bis(4-tert-butylcyclohexyl)thallium chloride. Thallium does not have a very strong preference for equatorial positions in dicyclohexylthallium chloride, whereas bis(4-alkylcyclohexyl)thallium chlorides exist largely in one conformation. Bis(4-methylcyclohexyl)thallium chloride exists in three isomeric forms; the major product appears to be the cis-isomer (equatorial methyl, axial thallium), with the other two isomers probably containing thallium trans to the methyl group (axial thallium being preferred). The preference for the cis-isomer (equatorial tert-butyl, axial thallium) of bis(4-tert-butylcyclohexyl)thallium chloride is such that other isomers are not obtained.     

Bis-thallium(I) porphyrin complexes

Treatment of octaethylporphyrin ($\text{1}$) or tetraphenylporphyrin ($\text{2}$) with more than two equiv of thallium(I) ethoxide gives the corresponding stable bis[thallium(I)] porphyrin complexes ($\text{5}$) and ($\text{6}$), respectively; these thallium(I) porphyrins are shown to have very different chemical and spectroscopic properties than do the corresponding thallium(III) porphyrin complexes.     

Preparation and Characterisation of a New Thallium(I) Uranate(VI), Tl4UO5

A new thallium(I) uranate(VI) of composition Tl₄UO₅ was isolated and characterised by X-ray, i. r. and chemical analyses. The compound dissociated into thallium(I) oxide and Tl₂UO₄ on heating to 230°C and its subsequent thermal behaviour depended on the volatilisation and oxidation characteristics of the thallium(I) oxide released.     

Influence of thallium(I) and thallium(III) on parameters of oscillating chemical reaction in a bromate-cerium(III,IV)-malonic acid-sulfuric acid system

The influence of thallium(I) and thallium(III) on the parameters of the Belousov-Zhabotinskii oscillating chemical reaction in the bromate-cerium(III, IV)-malonic acid-sulfuric acid system was studied. As a result of the addition of thallium(I) and thallium(III), the oscillation parameters change in the same way, which cannot be explained by the complexation of these ions with the bromide only. It was found that during the oscillating reaction, thallium(I) can be oxidized by bromine-containing compounds and thallium(III) reduced by the transformation products of malonic and bromomalonic acids. A scheme of action of a thallium(III)/thallium(I) two-electron redox pair in the oscillating chemical reaction studied has been proposed.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 23, No. 1, pp. 106–111, January–February, 1987.     

Spectrofluorometric determination of thallium(III) with pyrogallol red and 3,4,5,6-tetrachlorofluorescein

Summary A spectrofluorophotometric determination of thallium(III) is proposed. It is based on the enhancement of the fluorescence reaction of 3,4,5,6-tetrachlorofluorescein (TCF) with Pyrogallol Red (PR) by thallium(III) in the presence of Swanol (AM 301, lauryldimethyl aminoacetic acid betain) as an amphoteric surfactant. The method was found to be suitable for the determination of thallium(III) down to 4.0 g in 10.0 ml by measuring the difference in the relative fluorescence intensities of a TCF/PR/thallium(III) solution and a TCF/PR solution. The recovery test in artificial urine was satisfactory (96±2%).     

Determination of thallium(III) with novel arsenoxylphenylazo rhodanine after pre-concentration and separation

A new catalytic kinetic fluorescent method for determination of trace thallium(III) was investigated. The method was based on the catalytic effect of thallium on oxidation of 3-p-chlorophenyl-5-(2′-arsenoxylphenylazo) rhodanine (4ClRAAP) by hydrogen peroxide in potassium hydrogen phthalate-hydrochloric acid (pH?=?5.2). Under the optimum conditions the great increase of fluorescence intensity had a linear relationship against the concentration of thallium in the range of 0.43 to 10.0?µg?L^?1 with a detection limit of 2.6?×?10^?10?g?L^?1. The coexistent metal ions can be separated, and thallium can be enriched by polyamide, which greatly improved the selectivity and sensitivity of the system. The method was applied to determine trace amount of thallium in wine, water and mineral samples, with satisfactory results.     

Sequential oxidimetric determination of thallium(I) and (III)

The reaction between thallium(III) and oxalic acid in sulphuric acid medium has been investigated. Spectrophotometric results show that thallium(III) can be quantitatively reduced to thallium(I) with oxalic acid in aqueous medium when heated to near boiling point. Conditions for the estimation of the excess of oxalic acid with cerium(IV) sulphate in the presence of thallium(I) and for the estimation of a mixture of thallium(I) and thallium(III) have been investigated. The method is simpler than many other redox methods reported for the determination of thallium(III) and is free from many interferences encountered in these titrations. The reagents are cheap and quite stable.     

A new entry to N-heterocyclic carbene chemistry: synthesis and characterisation of a triscarbene complex of thallium(I)

The synthesis and characterisation of a thallium(I) triscarbene complex of the chelating, tripodal carbene ligand 1,3,5-[tris(3-tert-butylimidazol-2-ylideno)methyl]-2,4,6-trimethylbenzene is reported, in which the thallium ion is coordinated by three N-heterocyclic carbene donors in a distorted trigonal planar environment.     

A Prussian blue-based reactive electrode (reactrode) for the determination of thallium ions

A reactive electrode (reactrode) made of Prussian blue (PB), graphite and paraffin can be used for a selective determination of thallium ions down to a concentration of 2 · 10^–8 mol 1^–1. The working principle of the reactrode is that thallium ions can be pumped into Prussian blue during alternating oxidation-reduction cycles. After a preconcentration of thallium ions in PB, the voltammetric determination follows as usually in anodic stripping voltammetry, i.e. the thallium ions are reduced to thallium metal which is subsequently oxidized to give the anodic stripping signal. The peculiarity of the Prussian blue-thallium system is that the thallium ions are situated in the holes of the PB matrix. When reduced to metallic thallium, they are substituted by potassium ions. Cd²⁺, Fe³⁺, Zn²⁺, Cu²⁺ and Ni²⁺ do not interfere up to a hundredfold excess, NH₄⁺ does not interfere up to a thousandfold – and Bi³⁺ up to tenfold excess. The interference by Pb²⁺ can be suppressed with EDTA.     

Solubility, complex formation, and redox reactions in the Tl2O3-HCN/CN(-)-H2O system. Crystal structures of the cyano compounds Tl(CN)3.H2O, Na[Tl(CN)4].3H2O, K[Tl(CN)4], and Tl(I)[Tl(III)(CN)4] and of Tl(I)2C2O4

Thallium(III) oxide can be dissolved in water in the presence of strongly complexing cyanide ions. Tl(III) is leached from its oxide both by aqueous solutions of hydrogen cyanide and by alkali-metal cyanides. The dominating cyano complex of thallium(III) obtained by dissolution of Tl2O3 in HCN is [Tl(CN)3(aq)] as shown by 205Tl NMR. The Tl(CN)3 species has been selectively extracted into diethyl ether from aqueous solution with the ratio CN-/Tl(III) = 3. When aqueous solutions of the MCN (M = Na+, K+) salts are used to dissolve thallium(III) oxide, the equilibrium in liquid phase is fully shifted to the [Tl(CN)4]- complex. The Tl(CN)3 and Tl(CN)4- species have for the first time been synthesized in the solid state as Tl(CN)3.H2O (1), M[Tl(CN)4] (M = Tl (2) and K (3)), and Na[Tl(CN)4].3H2O (4) salts, and their structures have been determined by single-crystal X-ray diffraction. In the crystal structure of 1, the thallium(III) ion has a trigonal bipyramidal coordination with three cyanide ions in the equatorial plane, while an oxygen atom of the water molecule and a nitrogen atom from a cyanide ligand, attached to a neighboring thallium complex, form a linear O-Tl-N fragment. In the three compounds of the tetracyano-thallium(III) complex, 2-4, the [Tl(CN)4]- unit has a distorted tetrahedral geometry. Along with the acidic leaching (enhanced by Tl(III)-CN- complex formation), an effective reductive dissolution of the thallium(III) oxide can also take place in the Tl2O3-HCN-H2O system yielding thallium(I), while hydrogen cyanide is oxidized to cyanogen. The latter is hydrolyzed in aqueous solution giving rise to a number of products including (CONH2)2, NCO-, and NH4+ detected by 14N NMR. The crystalline compounds, Tl(I)[Tl(III)(CN)4], Tl(I)2C2O4, and (CONH2)2, have been obtained as products of the redox reactions in the system.     

Application of matrix-modification in determination of thallium in waste water by graphite-furnace atomic-absorption spectrometry

A method has been developed for the determination of thallium in waste water at the ng ml level by graphite-furnace atomic-absorption spectrometry. If microgram amounts of palladium or platinum are used as a matrix modifier, the ashing temperature for thallium can be raised to 1000 degrees , and the interference of halides and mineral acids is greatly reduced. The relative standard deviation found was 2% (9 replicate determinations) at the 8-ng ml thallium level, and the detection limit 1 ng ml .     

Determination trace amounts of thallium after separation and preconcentration onto nanoclay loaded with 1-(2-pyridylazo)-2-naphthol as a new sorbent

A procedure has been proposed for the separation and preconcentration of trace amounts of thallium. It is based on the adsorption of thallium ions onto organo nanoclay loaded with 1-(2-pyridylazo)-2-naphthol (PAN). Thallium ions were quantitatively retained on the column in the pH range of 3.5–6.0, whereas quantitative desorption occurs with 5.0?mL of 5% ascorbic acid and thallium was determined by flame atomic absorption spectrometry. Linearity was maintained between 0.66?ng?mL^?1–15.0?µg?mL^?1?in initial solution. Detection limit was 0.2?ng?mL^?1?in initial solution and preconcentration factor was 150. Eight replicate determinations of 2.0?µg?mL^?1 of thallium in final solution gave a relative standard deviation of ±1.48%. Various parameters have been studied, such as the effect of pH, breakthrough volume and interference of a large number of anions and cations and the proposed method was used to determine thallium ions in water and standard samples. Determination of thallium ions in standard sample showed that the proposed method has good accuracy.