Adducts of Gallium Trichloride and Bis(trimethylsilyl)sulfur Diimide

The monoadduct of GaCl 3 with bis(trimethylsilyl)sulfur diimide ( 1 ) was synthesized and fully characterized. In the attempt to synthesize and isolate the diadduct of bis(trimethylsilyl)sulfur diimide ( 2 ), an astonishing GaCl 3 diadduct of 3,3,5,5 ‐tetramethyl‐4,3,5,1,2,6‐oxadisilathiadiazine ( 3 ) was obtained. The formation of the six‐membered heterocycle can be explained by a methyl/chlorine exchange with GaCl 3 as transfer reagent followed slow hydrolysis along with a condensation process. The structure of 1 and 3 was determined by single crystal X‐ray studies ( 1 : monoclinic, P 2 1 /c, a = 11.187(2) Å, b = 9.338(2) Å, c = 18.117(6) Å, β = 111.80(2)° V = 1757.2(8) Å 3 , Z = 4; 3 : monoclinic, C 2/c, a = 19.950(6) Å, b = 8.722(2) Å, c = 12.078(2) Å, β = 114.60(4)°; V = 1910.8(8) Å 3 , Z = 4).