Group 4 Metal and Lanthanide Complexes in the Oxidation State +3 with Tris(trimethylsilyl)silyl Ligands

[Image: see text] A number of paramagnetic silylated d(1) group 4 metallates were prepared by reaction of potassium tris(trimethylsilyl)silanide with group 4 metallates of the type K[Cp(2)MCl(2)] (M = Ti, Zr, Hf). The outcomes of the reactions differ for all three metals. While for the hafnium case the expected complex [Cp(2)Hf{Si(SiMe(3))(3)}(2)](−) was obtained, the analogous titanium reaction led to a product with two Si(H)(SiMe(3))(2) ligands. The reaction with zirconium caused the formation of a dinuclear fulvalene bridged complex. The desired [Cp(2)Zr{Si(SiMe(3))(3)}(2)](−) could be obtained by reduction of Cp(2)Zr{Si(SiMe(3))(3)}(2) with potassium. In related reactions of potassium tris(trimethylsilyl)silanide with some lanthanidocenes Cp(3)Ln (Ln = Ce, Sm, Gd, Ho, Tm) complexes of the type [Cp(3)Ln Si(SiMe(3))(3)](−) with either [18-crown-6·K](+) or the complex ion [18-crown-6·K·Cp·K·18-crown-6] as counterions were obtained. Due to d(1) or f(n) electron configuration, unambiguous characterization of all obtained complexes could only be achieved by single crystal XRD diffraction analysis.