Thallium I oxide

In the absence of oxygen, gallium and indium are unaffected by water. Thallium, the most metallic element in Group III, reacts slowly with hot water and readily with steam to produce thallium(I) oxide, TI2O. 

In moist air, thallium slowly oxidizes to thallium(I) oxide [1314-12-1]. Steam and air or oxygen react readily with thallium forming thallium (1) hydroxide [12026-06-1]. Thallium dissolves only slowly in sulfuric or hydrochloric acid and the resultant salts have low solubilities. It is not soluble in alkaline solutions. 

Thallium(I) oxide, T120, is a well-characterized compound and a useful source of Tl+ salts.1 Matrix isolation studies of the solid gave structural data in agreement with spectroscopic results.290,291 The so-called peroxide T102 is obtained electrochemically from aqueous T12S04, but the properties include insolubility in water, alkali and some dilute adds, and treatment with dilute HC1 yields oxygen. The stoichiometry suggests that the compound is in fact a superoxide, and this has been confirmed by spectroscopic studies on frozen matrices.292,293... 

Thallium(I) oxide, T120, has a monoclinic modification, Q h, C2/m, a = 6.082, b = 3.52, c = 13.24 A, and p = 108.2°, with four molecules in the unit cell. Figure 5.63 shows the T1 atoms in close-packed layers in an AB sequence. Alternate O layers are filled by oxygen atoms giving the notation 2 3/2POP(m). The octahedra share edges. This is an unusual structure with oxygen atoms in octahedra. The Tl-O distances are 2.511-2.531 A. The Tl-Tl distances within a plane are 3.514 A, within... 

The sonication of an aqueous solution of TICI3 under a flow of argon led to a precipitate, composed of two products. The major product is TI2OCI2, while TI2O is obtained in small quantities. The latter has the structure of a multi-shell closed compound. The identification of the inorganic fullerenes in the TEM picture as the thallium (I) oxide is based on SAED measurements. In Eigure 6.5 we present a picture of the ortion-like IE. 

They reasoned that thallium(I) oxide is an intermediate and then carried out the reaction in refluxing ethanol2 to trap thallium(I) oxide as a stable thallium(I) derivative ... 

Thallium(I) oxide is soluble in water and the resulting hydroxide is as strong a base as KOH. 

A variant of the Williamson reaction for the preparation of ethers utilizes thallium ethoxide to convert the vicinal hydroxy groups in tartaric esters to the thallium(I) oxide derivative 590, which upon treatment with alkyl halides provides excellent yields of dialkylated tartaric esters 569 [189]. 

Water. Thallium(I) oxide reacts with H2O to form yellow TlOH, which dissolves up to 1.5 M at 20 °C. Thallium(III) oxide is insoluble in H2O and is only sUghtly affected when boiled with it. 

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