Thallium metal reactions with

B. Reaction of a Thallium Metal Carbonylate with a Silicon Halide. .. 11... 

Thallium(III), particularly as the trifluoroacetate salt, is also a reactive electrophilic metallating species, and a variety of synthetic schemes based on arylthallium intermediates have been devised.75 Arylthallium compounds are converted to chlorides or bromides by reaction with the appropriate cupric halide.76 Reaction with potassium iodide gives aryl iodides.77 Fluorides are prepared by successive treatment with potassium fluoride and boron trifluoride.78 Procedures for converting arylthallium compounds to nitriles and phenols have also been described.79... 

Thallium(i) salts have long been used in reactions with organic and organometallic halide complexes as a means of activating the halide by removal as insoluble T1X. However, the thallium ions proved not to be innocent bystanders, and numerous examples were reported in COMC (1995) where the metal-bound thallium complexes were formed. Deliberate reactions of thallium(i) and thallium(m) salts with metal carbonyl anions have yielded a variety of complexes of the form T1 MLJ3. In the past decade, new examples of metal carbonyl derivatives of thallium have been prepared (see Table 2). In addition, the propensity for Tl+ to form adducts with 16-electron noble metal complexes has been exploited. 

The physical properties of the metal (Table II) resemble those of thallium, lead and bismuth, its neighbors in the Periodic Table, rather than those of tellurium, its lower homologue. The low melting and boiling points are particularly noteworthy an attempted study of the Hall effect in polonium metal has also been reported (90). In chemical properties the metal is very similar to tellurium, the most striking resemblance being in its reactions with concentrated sulfuric acid (or sulfur trioxide) and with concentrated selenic acid. The products are the bright red solids, PoSOs and... 

Of the metals that form luminescent supramolecular entities with gold, that for which most complexes are known is thallium in its +1 oxidation state. As described below, in recent years the contributions of several laboratories have been reported. Nevertheless, in some cases, the papers also report similar reactions with other metals, leading to similar structures. In order to maintain a congruent synthetic description, those examples will be discussed together as they appear in the original work. 

The heterocycles react directly with alkali metals or undergo exchange reactions with, for example, sodium amide and hydride, n-butyllithium and thallium ethoxide, to form the TV-heteroaryl salts. The salts of the alkali metals exist as solvent separated ion-pairs or as contact ion-pairs (71JOC3091), as do the quaternary ammonium salts, whereas the salts of the heavier metals are generally considered to have a high N—metal covalent character. These characteristics, which can be modified by a change in the polarity of the solvent, control the reactions of the heteroaryl anions. 

Adducts of triazoles with transition metal salts are usually prepared by direct reactions between the two components involved and frequently precipitate or crystallize spontaneously from the reaction mixture (55,172,194, 202). Complexes containing triazolate anions can usually be obtained from the corresponding transition metal halide, carboxylate, nitrate, or perchlorate complex and an alkali metal (146, 147, 172) or thallium(I) triazolate salt (33). Other routes to triazolate complexes include the direct reactions of metal halides with triazoles in the presence of a base (201) and the treatment of triazole/metal halide... 

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