A Free Silanide from Nucleophilic Substitution at Silicon(II)

Chemistry. 2018 Aug 22;24(47):12236-12240. doi: 10.1002/chem.201801435. Epub 2018 Apr 30.

Abstract

A computationally guided synthetic route to a free silanide derived from tris(3-methylindol-2-yl)methane ([(tmim)Si]- ) through nucleophilic substitution on the SiII precursor (Idipp)SiCl2 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 PMe3. Experimentally, the [(tmim)Si]- anion is shown to undergo clean complexation to the base metal salts CuCl and FeCl2 , demonstrating the potential utility as a supporting ligand.

Keywords: constrained geometry; density functional theory; metal complexes; silicon; silyl ligand.