Reactions of GeCl 2 with the Thiolate LiSC(SiMe 3 ) 3 : From thf Activation to Insertion of GeCl 2 Molecules into C−S Bonds

The reaction system GeCl 2 ⋅ dioxane/LiSTsi (Tsi=C(SiMe 3 ) 3 ) opens a fruitful area in germanium chemistry, depending on the stoichiometry and solvent used during the reaction. For example, the reaction of GeCl 2 ⋅ 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 (H 7 C 4 O)Ge[STsi](μ 2 ‐S) 2 Ge[STsi] 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)Ge[S‐GeCl 2 ‐Tsi] 2 , in which additional GeCl 2 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 .