The Synthesis of Tris(silyl)silanides Revisited. A Study of Reactivity and Stability

Abstract

AbstractIn this contribution, we investigated the stability of (H3Si)3SiLi (2a) in the presence of tetramethylethylenediamine (TMEDA) and 1,2‐bis(diphenylphosphino)ethane (DPPE). Moreover, the synthesis to obtain tris(silyl)silanides with alternated counter ions by the base mediated desilylation approach was described. Additionally, metal‐metal exchange reactions of 2 a with MgBr2, ZnCl2, HgCl2 were examined. Subsequently, we reacted 2 a with 1.0 and 0.5 equivalents of ZnCl2[TMEDA] and could obtain the isolable zinc substituted silanides 5 a,b. Finally, we reacted 2 a with equimolar amounts of [(MesNacnac)MgI(OEt2)] and [(DippNacnac)MgI(OEt2)] and found the selective transmetalation to the corresponding magnesium substituted silanides 6 a,b in good yields. Interestingly, for compounds 5 a,b and 6 a,b the removal of the reaction solvents did not induce a degradation. For compound 6 a crystals suitable for X‐ray analysis could be grown, which represents the first structural characterization of an isolable perhydrogenated hypersilanide.