The oxidation reactions of ArSb [Ar = 2,6-(HC=N-t-Bu)₂C₆H₃] with S₈, grey Se and Te as well as E₂Ph₂ (E = S, Se, Te) are demonstrated. The reactions of ArSb with elemental sulfur and selenium occurred at elevated temperatures and yielded ArSbE (E = S, 1; Se 2), whereas the reactions with E₂Ph₂ proceeded at room temperature with subsequent formation of the corresponding insertion complexes ArSb(E₂Ph₎₂ (E = S 3; Se 4). In addition, ArSb(TePh)2 (5) was formed at very low temperature and showed a temperature-dependent reversible equilibrium with ArSb and Te2Ph₂ between – 80 ℃ to 20 ℃. The formation and structure of compounds 1 – 4, which were isolated in good yields, are assigned through multinuclear NMR (¹H, ¹³C, ⁷⁷Se), IR spectroscopy and microanalyses data. In addition, the molecular structures of 2 – 4 are further confirmed by single crystal X-ray diffraction studies.

Dedicated to Prof. G. van Koten on the occasion of his 75th birthday.