Nitrile formation via dichlorocarbene insertion into the Si-N bond of Ln(III) bis(trimethylsilyl)amide complexes.

The reactions of Ln[N(SiMe3)2]3 (Ln = Eu, Sm, Yb) with chloroform yield the [Ln{N(SiMe3)2}2(μ-Cl)(NCSiMe3)]2 (Ln = Eu(1), Sm(2)) and Yb[N(SiMe3)2]3(NCSiMe3)2 (3) complexes, all of which contain two neutral Me3SiCN ligands. The unexpected formation of the Me3SiCN ligand represents a rare example of nitrile formation through the insertion of dichlorocarbene into the Si-N bond.