A Free Silanide from Nucleophilic Substitution at Silicon(II).

A computationally guided synthetic route to a free silanide derived from tris(3-methylindol-2-yl)methane ([(tmim)Si] ) through nucleophilic substitution on the Si precursor (Idipp)SiCl is reported (Idipp=2,3-dihydro-1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-2-ylidene). This approach circumvents the need for strained tetrahedral silanes as synthetic intermediates. Computational investigations show that the electron-donating properties of [(tmim)Si] are close to those of PMe Experimentally, the [(tmim)Si] anion is shown to undergo clean complexation to the base metal salts CuCl and FeCl , demonstrating the potential utility as a supporting ligand.

Hydrosilylation in Aryliminopyrrolide-Substituted Silanes.

A range of silanes was synthesized by the reaction of HSiCl3 with iminopyrrole derivatives in the presence of NEt3 . In certain cases, intramolecular hydrosilylation converts the imine ligand into an amino substituent. This reaction is inhibited by factors such as electron-donating substitution on Si and steric bulk.