Two tetraalkoxy‐λ4‐telluranes were prepared from tellurium tetrachloride and the sodium salts of methanol and 2,2,2‐trifluoroethanol, respectively. Their molecular structures which were determined by single‐crystal X‐ray diffraction show dipolar intermolecular contacts. NBO analyses for the title compounds were conducted to assess the role of the stereochemically active lone pair on the tellurium atoms.
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