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, AlCl3, AlBr3 (5−8), a bis‐N adduct with InCl3 (9), and the corresponding dithiazinanium salts with the anions AlBr4−, AlCl4−, 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. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)