Synthèses et analyses structurales de perchlorates anhydres d'In(III) et de Tl(III) M(ClO₄)₃ et ClO₂M(ClO₄)₄; (M = In, Tl)

Reactions of chlorine trioxide (Cl2O6) with anhydrous InCl3, TlCl3, and InCl3•4H2O have been investigated. They give two chloryl perchlorato metallates: ClO2In(ClO4)4 and ClO2Tl(ClO4)4, which can be decomposed on heating (80 °C) under dynamic vacuum. They yield respectively In(ClO4)3 and Tl(ClO4)3. Tl(ClO4)3 appears to have weaker thermal stability than In(ClO4)3, which is stable up to 272 °C; the former decomposes starting at 95 °C to give TlO0.5(ClO4)2. In(ClO4)3 and Tl(ClO4)3 have the same space group [Formula: see text]. The best assignment of their ir and Raman vibrational spectra can be made on the basis of a polymeric structure (Asl3 type) with bridging bidentate perchlorato groups strongly bonded to the metal. The ClO2M(ClO4)4 (M = In, Tl) salts are well defined. The cation ClO2+ is unambiguously characterized; it interacts with the anion M(ClO4)4−, which has monodentate and bidentate perchlorate groups.