Group 13 complexes of 5-methyl-1,3,5-dithiazinane

The synthesis of mono-N adducts of 5-methyl-1,3,5-dithiazinane (1) with Al(CH₃)₃, Al(CH₃)₂Cl, AlCl ₃, AlBr₃ (5-8), a bis-N adduct with InCl₃ (9), and the corresponding dithiazinanium salts with the anions AlBr₄ ^-, AlC₄^-, GaCl₄^- and BCl₄^- (10-14) are reported. Compounds 5-7 adopt a preferred conformation in solution at room temperature and 8 at -10 °C. ΔG^≠ values for the ring inversion were calculated for 5-8. Compounds 6-14 were studied by single-crystal X-ray diffraction. The solution and solid-state analyses showed that the rings are present in all cases in a chair conformation. In compounds 5-8 the tetrahedral aluminum atom is found in an equatorial position. In the indium compound 9 the metal atom has a tbp geometry. For dithiazinanium rings 10-14 dipolar intra- and intermolecular interactions between halogen atoms and C-H and N-H are reported. Two different conformations for the N-CH₃ were found in compound 14.