Structure and Properties of an Overcrowded 1,2-Dibromodigermene

A 1,2-dibromodigermene having Bbt groups (Bbt = 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl) was synthesized by the reaction of BbtLi with GeBr2·dioxane. X-ray crystallographic analysis revealed that it retains the GeGe double bond in the solid state, while the equilibrium between the 1,2-dibromodigermene and the corresponding bromogermylenes in solution was evidenced by the UV−vis spectroscopic studies and the chemical reactions. The reactions of the 1,2-dibromodigermene with elemental sulfur in toluene resulted in the formation of a cis-dithiadigermetane derivative, indicating the generation of a transient germathiocarbonyl bromide derivative via the sulfurization reaction of the Bbt-substituted bromogermylene generated in the equilibrium state.