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 (H7 C4 O)Ge[STsi](μ2 -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-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 .