Thallium I Azide

TIN3 has one nasty property which requires attention Its sensitivity to friction depends on the sample thickness and is highest in very thin layers. Pointed out by Wohler and Martin [115] as early as 1917, this fact went grossly unnoticed and has resulted in several unnecessary accidents in laboratories. Thallium(I) azide should be handled with the same safety precautions that apply to lead azide. 

TIN3 is one of the few metal azides that melt (MP in vacuo, 330°C) prior to decomposition. At 340°C it begins to sublime, evolves gas at 370°C, and explodes at 430°C, leaving silver-white thallium metal as residue [2]. It is only slightly soluble in cold water. 

The compound is obtained very easily by admixing a soluble azide to an aqueous thallium(I) salt solution. The product precipitates immediately as a straw-yellow crystal powder. Larger crystals are obtainable by cooling hot, saturated aqueous solutions [62]. Combinations such as thallium sulfate/ potassium azide [237] and thallium nitrate/ammonium azide [61] may be used for the preparation. This author prefers thallium perchlorate and sodium azide, because favorable solubility products of the ions involved and the absence of hydration lead to a material that is free of coprecipitated ions. For example, to a stirred solution of 200 g TICIO4 in 1600 ml water is admixed 45 g sodium azide dissolved in 150 ml water. The dense precipitate is washed with cold water until perchlorate free, and then with acetone. Practical yield, 152 g. The product should be stored completely dry as the damp material tends to discolor [236]. 

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Thallium hydroxyoxodiperoxochromate(l—), 4222 Thallium(I) azide, 4760 Thallium(I) chlorite, 4037... 

Thallium(i) azide and iodine converted 5a-cholest-2-ene into a mixture of three isomeric iodo-azides. Reaction of either a 17-methyleneandrostane (77) or a 17-methylandrost-16-ene (78) with thallium triacetate gave mixtures of the allylic acetates (79), (80), and (81). Oxymercuration-demercuration was more selective in giving, after acetylation, the 16/8-acetoxy-17-methylene compound (80) as the main product. 

Thallium (I) azide has the body-centered tetragonal structure of potassium, rubidium, and cesium azides (see Chapter 3), but it differs in being an easily initiated explosive, as well as having its fundamental optical absorption at lower energy (3.6 eV vs. approximately 8 eVfor KN3, RbNa, andCsNa see Chapter 5). It is of interest to investigate the effect of this difference in electronic structure on the ESR spectra of defects in the four materials having the same crystal structure. 

Cadmium azide Copper (I) azide Lead azide Mercury (II) azide Silver azide Thallium (I) azide Potassium azide... 

The action of thallium(i) azide and iodine on alkenes gives different product ratios from those given by sodium azide and iodine chloride. Iodine azide does not appear to be preformed and solvent incorporation can occur when acetonitrile is the solvent (Scheme 50). Methyliodine(iii) difluoride reacts with phenylsubstituted... 

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