Reactions of GeCl2 with the Thiolate LiSC(SiMe3)3: From thf Activation to Insertion of GeCl2 Molecules into C?S Bonds

The reaction system GeCl₂ ? dioxane/LiSTsi (Tsi=C(SiMe₃)₃) opens a fruitful area in germanium chemistry, depending on the stoichiometry and solvent used during the reaction. For example, the reaction of GeCl₂ ? dioxane in toluene with two equivalents of the thiolate gives the expected germylene Ge(STsi)₂ in excellent yield. This germylene readily reacts with hydrogen and acetylene, however, in a non-selective way. By using an excess amount of the thiolate and toluene as the solvent, the germanide Ge(STsi)₃]Li(thf)] is obtained. Performing the same reaction in thf leads to a C?H activation of thf to give (H₇C₄O)GeSTsi](μ²-S)₂GeSTsi]₂, in which the thf molecule is still intact. Using a sub-stoichiometric amount of the thiolate leads to the heteroleptic compound ClGe(STsi)]₂ and to the insertion product (thf)GeS-GeCl₂-Tsi]₂, in which additional GeCl₂ molecules insert into the C?S bonds of Ge(STsi)₂. The synthesis and the experimentally determined structures of all compounds are presented together with first reactivity studies of Ge(STsi)₂.