Coordination and Stabilization of a Lithium Ion with a Silylene

Abstract Herein, we report the stabilization of lithium‐ion as the source of lithium to use as a trans‐metalation reagent [{PhC(N t Bu) 2 Si( t Bu)Li} 2 I( t BuN) 2 CPh] ( 1 ). The reaction of 3 equivalents of the LSi t Bu (L=PhC(N t Bu) 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) 2 C at room temperature affords compound [PhC(N t Bu) 2 Si(Cl)(NCy) 2 NCy] ( 2 ) with the CN 2 SiN 2 C 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.