(RTe)(2) (R = 2,6-dimethoxyphenyl) reacted with iodine to give [RTeTeI(2)R] (1), [R(2)TeTeR(2)][Te(4)I(14)] (2), and [RTe(I)I(2)] (3). The synthesis of the mixed-valent, neutral complex 1 occurred easily through the reaction of (RTe)(2) with mesTeI (mes = 2,4,6-trimethylphenyl), which proved the ability of mesTeI to act as a selective oxidation reagent. In the cationic species [R(2)TeTeR(2)](2+) as well in the counterion [Te(4)I(14)](2-) of compound 2, tellurium occurs in the rare oxidation state 3+.

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Abstract(MesTe)2 and bromine or chlorine react with pyridinium bromide and pyridinium chloride to give (PyH)[mesTeBr2] (1), (PyH)[mesTeClBr] (2) and (PyH)[mesTeCl2] (3), respectively. The TeII atoms in 1, 2 and 3 adopt a three‐coordinate, T‐shaped configuration and the trans tellurium‐halogen bonds present different distances, since the X(1)‐halogens {Br (1), Cl (2, 3)} attain hydrogen bondings toward the N–H group of the pyridinium cations. The title compounds do not reproduce the dimeric assembling of some newly reported parent tellurium dihalides.

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