Thallium complexes fluorides

F4OW, Tungsten fluoride oxide, 24 37 F4SE, Selenium tetrafluoride, 24 28 FsCJH, Benzene, pentafluoro-cobalt complexes, 23 23-25 lithium and thallium complexes, 21 71,... 

Mercuration of aromatic compounds can be accomplished with mercuric salts, most often Hg(OAc)2 ° to give ArHgOAc. This is ordinary electrophilic aromatic substitution and takes place by the arenium ion mechanism (p. 675). ° Aromatic compounds can also be converted to arylthallium bis(trifluoroacetates), ArTl(OOCCF3)2, by treatment with thallium(III) trifluoroacetate in trifluoroace-tic acid. ° These arylthallium compounds can be converted to phenols, aryl iodides or fluorides (12-28), aryl cyanides (12-31), aryl nitro compounds, or aryl esters (12-30). The mechanism of thallation appears to be complex, with electrophilic and electron-transfer mechanisms both taking place. 

The values of AH for the thallium (III) halide systems becomes less exothermic as complex formation proceeds. There are no steps with about the same value of AH , in marked contrast to e.g. Hg2+ and Pd2+. The trend of AH is in fact opposite to that found for several t)q)ical hard-hard interactions, e.g. iron (III) fluoride, lanthanum sulphate and yttrium acetate (Table 1). An even more striking feature of the thallium (III) halides is that AS°n is approximately constant for all steps. This is indeed different not only from ions such as In +, Cd2+ and Zn +, where reversals of the decreasing trend of AS°n occur for certain steps, but also from Hg2+ and Pd + where the higher steps have a much lower value of ASn than the earlier ones. 

Silver, lead, copper(l). and thallium(I) thiocyanates are insoluble and mercuiy(II), bismuth, and tm(II) thiocyanates slightly soluble. All of these, are soluble in excess of soluble (e.g., ammonium) thiocyanate, forming complexes. Iron(III) thiocyanate gives a blood-red solution, used in detecting either Fe(lll) or thiocyanate in solution, and is extracted from water by amyl alcohol. It is not formed in the presence of fluoride, phosphate and other strongly complexing ions,... 

Chromium carbene complexes. phloroglucinols Malonyl dichloride. phthalides Thallium(III) trifluoroacetate. pinacols Samarium(II) iodide. Tetra-w-butylammonium fluoride. 

Thallium(I) halides are predominantly ionic, although there is a tendency toward increasing covalent character in the series of compounds TlCl (17%), TlBr (20%), and TII (28%). This increased degree of covalency results in decreased solubility for example, TIF is soluble in water whilst the other Tl halides are only sparingly soluble. The thallium(I) halides are classical examples of incompletely dissociated 1 1 electrolytes. The stability of halide complexes of Tl is low and follows the order TIF < TlCl < TlBr < TII, where for the series of halides, Kx = -, 0.8, 2.1, 5.0 and Ki = -, 0.2, 0.7, 1.5 respectively. The fluoride ion F is preferred to perchlorate as a noncomplexing counterion. Claims have been made for T1X species with n = 3 and 4 however, the formation of complexes in aqueous solution with n > 2 seems unlikely. 

Fluoride, chloride, bromide, and iodide derivatives of thallium(I) are well known. Their solubilities and photosensitivity are similar to the corresponding silver(I) systems. TIE is water-soluble, whereas the chlorides, bromides, and iodides are water-insoluble solids. This property is exploited in ligand-transfer chemistry involving thallium precursors. Some solid-state structures of thal-lium(I) salts of weakly coordinated anions show TT -halide interactions. Selective abstraction of a fluoride from a C-F bond, leading to thallium fluoride, has been described. The compound [ P(CH2CH2PPh2)3 RuH( 7 -ClTl)]PF6 represents the first metal complex containing an 77 -Cl-bonded TlCl ligand. This compound act as a thallium(I)-ion carrier. 

The crystal structures of the three heavier thallium(I) halides have been established and lattice energies calculated the inert pair of T1+ is apparently insignificant in terms of the stability of the lattice. The enthalpy of hydration of the Tl ion was also derived. Gas phase (TlBr, Til) and matrix isolation studies (TlCl, TlBr, Til) have shown that TlX and TI2X2 species are important.Complex formation in aqueous solution decreases in the order Cl > Br > I, and as with the fluorides, the double salts show no evidence of anionic complex formation by Tl Finally, it is important to note that TII3 is formulated as Tr(lT) from X-ray studies.Thermal decomposition yields TI3I4, whose structure has not been reported. 

Main and subgroup elements of the earlier rows often exhibit a dynamic equilibrium between different coordination numbers. Elements such as fluorine, chlorine, oxygen, etc., can donate one or two free electron pairs to vacant lower energy orbitals of these metal atoms. Fluorine can therefore act as a bifunctional bridging atom, and oxygen can even be mono- to tetrafunctional, according to its bond partner. In all these cases the coordination number is increased above normal. In the case of fluorine, fluorine bridge bonds exist, for example, in the anion of the complex between thallium fluoride and aluminum fluoride ... 

A cyanide supporting electrolyte Is useful for determining lead in the presence of large amounts of cadmium because the wave of the lead-cyanide complex precedes that of the cadmium complex by about 0.4 V (K5). Bismuth, antimony, - l ead and tin mixtures have been determined using a hydrochloric acld-sodlum fluoride supporting electrolyte (l6). The use of an ammonlacal tartarate soln has been found to be beneficial for the simultaneous determination of thallium and lead (B2). 

Singh, S.S. and Brydon, J.E. (1969) Solubility of basic aluminium sulfates at equilibrium in solution and in the presence of montmorillonite. Soil ScL, 107, 12—16. Sipos, P., Capewell, S.G., May, P.M., Hefter, G.T, Laurenczy, G., Lukacs, F., and Roulet, R. (1997) tI-NMR and UV-Vis spectroscopic determination of the formation constants of aqueous thallium(l) hydroxo-complexes. J. Solution Chem., 26, 419-431. Srinivasan, K. and Rechnitz, G.A. (1968) Reaction rate measurements with fluoride ion-selective membrane electrode. Formation kinetics of ferrous fluoride and aluminium fluoride complexes. Anal. Chem., 40, 1818-1825. 

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