A Free Silanide from Nucleophilic Substitution at Silicon(II)

A computationally‐guided synthetic route to the free silanide derived from tris(3‐methylindol‐2‐yl)methane ((tmim)Si‐) is reported: nucleophilic substitution on the Si(II) precursor Idipp‐‐>SiCl2 (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 its potential utility as a supporting ligand