Silyl Transfer Pathway to a Ce(IV) Imido Complex

The formation and stabilization of multiple bonds between a lanthanide cation and an anionic p-block element fragment are challenging, and only a few examples of such terminal complexes have been reported to date. Notably, all reported synthetic routes to lanthanide-imido moieties employed deprotonation as the key formation step. In the present report, we describe the generation of a Ce(IV) imido complex by a trimethylsilyl group transfer pathway. Experimental and computational evidence supports an equilibrium proceeding by a bimolecular nucleophilic substitution mechanism.