Chemie polyfunktioneller liganden: LXXIII. Synthese,struktur und reaktionsverhalten von cryptanden (bzw. spheranden) mit den heteroelementen arsen,sauerstoff, schwefel und stickstoff

The reaction of N(CH₂CH₂Cl)₃ (I) with KAs(C₆H₅)₂·dioxane ($\text{1}\text{2}$) in THF yields, as Sacconi et al. reported earlier, 80% of NCH₂CH₂As(C₆H₅)₂]₃ (II). II is now obtained in a still higher quantity from the reaction of HN(CH₂CH₂Cl)₃]Cl (III) with NaAs(C₆H₅)₂ in liquid ammonia. Treatment of II with gaseous HI in dry CH₂Cl₂ results in the formation of HN(CH₂CH₂AsI₂)₃]I (IV), which is isolated by recrystallisation from THF as HN(CH₂CH₂AsI₂)₃]I · THF ($\text{1}\text{1}$) (IVa). IVa reacts with H₂O/NH₃ or H₂S/N(C₂H₅)₃ to give the novel cryptands N(CH₂CH₂)₃]₈-(As₄O₄)₆ (V) or N(CH₂CH₂)₃]₈(As₄S₄)₆ (VI), which also can be denoted as spherands. The reaction of V with dry gaseous HCl in benzene leads to HN(CH₂-CH₂AsCl₂)₃]Cl (VII). All the new compounds are characterized, as far as possible, by their IR, FIR, Raman, ¹H NMR and mass spectra. To determine the structure of V a single X-ray crystal study was carried out. Moreover II, which is already well-known but not completely characterized, is included in this discussion only for spectroscopic comparison.