Synthesis and Characterization of Methoxylated Oligosilyl Group 4 Metallocenes

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)3Si]3SiK (1) underwent a selective monosubstitution to the respective...

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Published inInorganic chemistry Vol. 61; no. 37; pp. 14742 - 14751
Main Authors Sauermoser, Aileen, Lainer, Thomas, Glotz, Gabriel, Czerny, Frank, Schweda, Bettina, Fischer, Roland C., Haas, Michael
Format Journal Article
LanguageEnglish
Published American Chemical Society 19.09.2022
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Summary: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)3Si]3SiK (1) underwent a selective monosubstitution to the respective oligosilyl-decorated metallocenes [(MeO)3Si]3SiMClCp2 (2–4). Surprisingly, the attempted disilylation with this silanide was not possible. However, in the case of titanocene dichloride, a stable radical [(MeO)3Si]3SiTiCp2 (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)3Si]2Si­(SiMe2)2Si­[(MeO)3Si]2K (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.
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ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.2c02112