Synthesis and Characterization of Methoxylated Oligosilyl Group 4 Metallocenes

[Image: see text] New methoxylated oligosilyl-substituted metallocenes were synthesized by the reaction of two oligosilanides with different metallocene dichlorides (M = Ti, Zr, and Hf). The first investigated tris(trimethoxysilyl)silanide [(MeO)(3)Si](3)SiK (1) underwent a selective monosubstitution to the respective oligosilyl-decorated metallocenes [(MeO)(3)Si](3)SiMClCp(2) (2–4). Surprisingly, the attempted disilylation with this silanide was not possible. However, in the case of titanocene dichloride, a stable radical [(MeO)(3)Si](3)SiTiCp(2) (5) was formed. The unsuccessful isolation of bisilylated metallocenes encouraged us to investigate the reactivity of another silanide. Therefore, we synthesized a hitherto unknown disilanide K[(MeO)(3)Si](2)Si(SiMe(2))(2)Si[(MeO)(3)Si](2)K (8), which was accessible in good yields. The reaction of compound 8 and different metallocene dichlorides (M = Ti, Zr, and Hf) gave rise to the formation of heterocyclic compounds 9–11 in good yields.