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

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