Nucleophilicity of Neutral versus Cationic Magnesium Silyl Compounds

Charge and ancillary ligands affect the reactivity of monomeric tris(trimethylsilyl)silyl magnesium compounds. Diamine-coordinated (tmeda)Mg{Si(SiMe3)3}Me (tmeda = tetramethylethylenediamine; 2-tmeda) and (dpe)Mg{Si(SiMe3)3}Me (dpe =1,2-N,N-dipyrrolidenylethane; 2-dpe) are synthesized by salt elimination reactions of L2MgMeBr and KSi(SiMe3)3. Compounds 2-tmeda or 2-dpe react with MeI or MeOTf to give MeSi(SiMe3)3 as the product of Si–C bond formation. In contrast, 2-tmeda and 2-dpe undergo exclusively reaction at the magnesium methyl group with electrophiles such as Me3SiI, B(C6F5)3, HB(C6F5)2, and [Ph3C][B(C6F5)4]. These reactions provide a series of neutral, zwitterionic, and cationic magnesium silyl compounds, and from this series we have found that silyl group transfer is less effective with cationic magnesium compounds than neutral complexes.