The synthesis and structural aspects of the perbromo-functionalised thiaboranes -SBBr ( = 5, 9, 11): the solid-state structure of the octahedral -SBBr, governed by strong dihalogen contacts.

Co-pyrolysis reactions of BBr with SBr at 350 °C yielded the brominated thiaboranes -SBBr (1), -1-SBBr (2) and -SBBr (3), confirmed by high-resolution mass spectrometry, experimental and computational B NMR spectroscopy. The strong Br(σ-hole)⋯Br(ring) attraction has been the decisive energy contribution in the crystal of 1.