Coordination and Stabilization of a Lithium Ion with a Silylene

Abstract

Abstract Herein, we report the stabilization of lithium‐ion as the source of lithium to use as a trans‐metalation reagent [{PhC(NtBu)2Si(tBu)Li}2I(tBuN)2CPh] (1). The reaction of 3 equivalents of the LSitBu (L=PhC(NtBu)2) and lithium iodide at low temperature leads to a silylene stabilized lithium‐ion with an additional coordination of amidinate ligand. Compound 1 shows two four membered and one six membered ring as confirmed by QTAIM calculations. Whereas the reaction of the LSiCl with 1.5 equivalents of carbodiimide (CyN)2C at room temperature affords compound [PhC(NtBu)2Si(Cl)(NCy)2NCy] (2) with the CN2SiN2C skeleton containing silicon as a central atom. Both the compounds were fully characterized by NMR, mass spectrometry, X‐ray crystallographic analysis, and quantum mechanical calculations. Stabilization effect: We have synthesized and characterized a silylene stabilized lithium ion 1. Compound 1 exhibits presence of two four‐ membered and one six‐ membered ring as confirmed by QTAIM calculations. Compound 2 shows unusual dissociation of carbodiimide to give two four‐membered rings containing a penta‐coordinated silicon as a central atom. Furthermore, the bond nature and stabilization of compound 1 were confirmed by quantum theory of atoms in molecules. image