Thallium thiolates

The cadmium thiolate complexes [Cd(Tm/ Tol)(SR)] (R = Bn, Ph, p-Tol, C6F5) were prepared by the reaction of [CdBr(Tm/ "To1)] with equimolar amounts of the corresponding thallium thiolates. [CdSPh(Tm/7"To1)] is a four-coordinate species exhibiting a distorted tetrahedral geometry in the solid state.53... 

A. Thallium T) 2-methylpropane-2-thiolate. A 500-mL, round-bottomed flask equipped with a magnetic stirring bar and a pressure-equalizing dropping funnel to which a nitrogen inlet adapter is attached is charged with 47.2 g (0.189 mol) of thallium(I) ethoxide (Note 1) and 200 mL of anhydrous benzene (Note 2). Over a period of 15 min 19.2 g (24 mL, 0.213 mol) of 2-methylpropane-2-thiol (Note 1) is added. The... 

Thallium(I) 2-methylpropane-2-thiolate 2-Propanethiol, 2-methyl-, thal-lium(I) salt (10) (56393-79-4)... 

Thallium(I) thiolates form polymers, often with complex structures. Thus TlSPh is ionic and best described as [Tl7(SPh)6]+[Tl5(SPh)6], while TISBu is an octameric cage.58 Numerous anionic polychalcogenide complexes are known, such as [Tl2Te2]2 and [T12(S4)2]2 (6-XXV).59 As expected for a soft metal, Tl—chalcogenide bonds are strong and highly covalent. 

Thallium(I) thiolates have been introduced by Masamune et Their use is especially advant-... 

The structures of four tri-t-butoxysilanthiolates 210-213 have been reported. Whereas 210 is tetrameric with a nearly planar eight-membered ring, 211 and 212 are dimeric. In addition to the two thiolate S atoms the thallium atoms in 211 are also coordinated, albeit more weakly, by one butoxy O atom at a distance of 2.799(4) A. A similar (2+1) coordination is found for the mercury atoms in the monomeric species 212 [d(Hg-O) = 2.878(4) A]. Remarkably short Si-S distances are found in 213 and, in particular, 211 [2.078(2) A], suggesting that the M-S bonds (M = Pb, Tl) may exhibit a marked degree of ionicity in these compounds. 

These reports further indicate that the detailed explanations of electronic transitions in thallium and lead alkali halides are general and can be applied to a wide variety of related systems, such as the sulfides and thiolates, both in the solid state and in aqueous solution. 

Thallium(l) thiolates have been introduced by Masamune et Their use is especially advantageous if 5-t-butyl thiocarboxylic esters are to be prepared which can serve as educts for macrolide synthesis. Zearalenone dimethyl ether ethylene acetal (22 cf. also Scheme 1) was obtained from the corresponding acid chloride and thallium(I) a-methylpropanethiolate via the S-f-butyl benzenecarbo-thioate (21 equation 14)... 

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