The stoichiometrically controlled chlorination of the diarylditelluride (8-Me2NC10H6Te)2 with SO2Cl2 afforded the aryltellurinyl chloride 8-Me2NC10H6TeCl (1) and the aryltellurium trichloride 8-Me2NC10H6TeCl3 (2). Alternatively, 1 was obtained by the reaction of the aryltellurenyl diethyldithiacarbamate 8-Me2NC10H6Te(S2CNEt2) with hydrochloric acid. The base hydrolysis of 2 provided the novel telluroxanes (8-Me2NC10H6Te)2OCl4 (3), (8-Me2NC10H6Te)6O5Cl8 (4), (8-Me2NC10H6Te)6O8Cl2 (5), [(8-Me2NC10H6Te)2O3]n (6) and (8-Me2NC10H6Te)6O8(OH)2 (7) depending on the reaction conditions applied. The reaction of 7 with ClTe(OiPr)3 in the presence of water gave rise to the telluroxane (8-Me2NC10H6Te)6Te2O12Cl2 (8). The crystal and molecular structures of 1–3 and 5–8 were determined by X-ray crystallography. The telluroxane clusters and polymers 6–8 hold potential as model compounds for alkali tellurite glasses (M2O)x(TeO2)1−x (M=Li, Na, K) for which no precise structural data are available.
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