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(CH 3 ) 3 , Al(CH 3 ) 2 Cl, AlCl 3 , AlBr 3 ( 5 − 8 ), a bis‐N adduct with InCl 3 ( 9 ), and the corresponding dithiazinanium salts with the anions AlBr 4 − , AlCl 4 − , GaCl 4 − and BCl 4 − ( 10 − 14 ) are reported. Compounds 5 − 7 adopt a preferred conformation in solution at room temperature and 8 at −10 °C. Δ G ≠ 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−CH 3 were found in compound 14 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)