Thallium complexes anionic derivatives

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. 

In addition to the halide systems there are a number of thallium(I) salts of thallium(III) complex anions in which the overall stoichiometry implies, incorrectly, the presence of thallium(II) species. These include the sulfate, selenate,369 acetate370 and oxalate371 derivatives. An X-ray determination has confirmed that Tl(OAc)2 is indeed Tl[Tl(OAc)4], in which the anions are linked through seven-coordinate Tl+, with some evidence for a stereochemically active inert pair.370 In T1[T1(0H)(S04)2], the structure consists of sheets of linked anions with Tl+ ions.372... 

Reaction of the anion 21 with Cp or Cp metal fragments provides further metallocene-type complexes with a pendant phosphaferrocene side-chain. For example, the reaction of the thallium derivative T1 21 with [Cp RhCl2]2 yields the cationic pentamethylrhodocenium 24 as its chloride (Scheme 1.5.10). This is an interesting species because it is a chiral water-soluble P ligand. The chloride anion can be exchanged by PF,s to make the compound more soluble in organic solvents. 

C6C15) with dimethylsulfoxide (DMSO), which leads to the synthesis of [Tl2 Au(C6F5)2 2 p-DMSO 3] or [Tl2 Au(C6Cl5)2 2 h-DMSO 2]ra, respectively.62 The crystal structure of the complex with fluorine shows a monodimensional polymer formed by repetition of [Au--Tl(p-0 = SMe2)3Tl] units, with gold-thallium interactions of 3.2225(6)-3.5182(8), while the pentachlorophenyl derivative contains two bridging DMSO molecules and an additional [Au(C6Cl5)2] anion. In addition, a thallium-thallium interaction of 3.7562(6) A appears in the latter (Fig. 21). 

The first thallium(I) n complexes with carbollide ligands were synthesized by Stone et al. (180) addition of an aqueous solution of thallium(I) acetate to an aqueous alkaline solution of the dicarbaundecaborane anion, 7,8-CzB, , or its C-alkyl derivatives causes the formation of the new compounds (LIVa-c) [Eq. (15)]. One of the thallium atoms in the air-stable,... 

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 anionic bis(l,2-arenedithiolato) titanium derivatives [Cp Ti(S2C6H3R)2]- (Cp = Cp, Cp, CsH4Me) (Scheme 419) have been prepared as the thallium(i) salts by the reaction of Cp TiCl3 and thallium dithiolate in THF. The molecular structures of the complexes have been determined by X-ray diffraction.1017 Thallium(i) derivatives of... 

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. 

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