Rare-Earth–Silyl ate-Complexes Opening a Door to Selective Manipulations

[Image: see text] The reactions of a number of rare-earth (RE) trichlorides and an oligosilanylene diide containing a siloxane unit in the backbone in DME are described. The formed products of the type [(DME)(4)·K][(DME)·RE(Cl)(2){Si(SiMe(3))(2)SiMe(2)}(2)O] (RE = Y, La, Ce, Pr, Sm, Tb, Dy, and Er) are disilylated dichloro metalate complexes and include the first examples of Si–La and Si–Pr compounds as well as the first structurally characterized example of a Si–Dy complex. A most intriguing aspect of the synthesis of these complexes is that they offer entry into a systematic study of the still largely unexplored field of silyl RE complexes by the possibility of ligand exchange reactions under preservation of the Si–RE interaction. This was demonstrated by the conversion of [(DME)(4)·K][(DME)·RE(Cl)(2){Si(SiMe(3))(2)SiMe(2)}(2)O] to [(DME)(4)·K][Cp(2)Y{Si(SiMe(3))(2)SiMe(2)}(2)O].