Six-vertex closo-SB5Cl5 (1) and ten-vertex closo-1-SB9Cl9 (2) thiaboranes have been prepared, besides the already known 12-vertex closo-SB11Cl11 (3), from the co-pyrolysis reaction of B2Cl4 with S2Cl2 at 280 ºC in vacuo. The compounds are sublimable, off-white solids. Their elemental composition has been determined by high-resolution mass spectrometry. They were further characterized by one- and two-dimensional 11B-spectroscopy and X-ray structure determination for 1 and 3. Ab …