甲氧基化低聚硅基第4族金属茂的合成与表征
Synthesis and Characterization of Methoxylated Oligosilyl Group 4 Metallocenes.
作者信息
Sauermoser Aileen, Lainer Thomas, Glotz Gabriel, Czerny Frank, Schweda Bettina, Fischer Roland C, Haas Michael
机构信息
Institute of Inorganic Chemistry, Graz University of Technology, Stremayrgasse 9/V, A-8010 Graz, Austria.
Institute of Physical and Theoretical Chemistry, Graz University of Technology, Stremayrgasse 9/II, 8010 Graz, Austria.
出版信息
Inorg Chem. 2022 Sep 19;61(37):14742-14751. doi: 10.1021/acs.inorgchem.2c02112. Epub 2022 Sep 1.
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)Si]SiK () underwent a selective monosubstitution to the respective oligosilyl-decorated metallocenes [(MeO)Si]SiMClCp (-). Surprisingly, the attempted disilylation with this silanide was not possible. However, in the case of titanocene dichloride, a stable radical [(MeO)Si]SiTiCp () 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)Si]Si(SiMe)Si[(MeO)Si]K (), which was accessible in good yields. The reaction of compound and different metallocene dichlorides (M = Ti, Zr, and Hf) gave rise to the formation of heterocyclic compounds - in good yields.
通过两种不同的茂金属二氯化物（M = Ti、Zr和Hf）与两种低聚硅化物反应，合成了新型甲氧基化低聚硅基取代的茂金属。首先研究的三（三甲氧基硅基）硅化物[（MeO）Si]SiK（）对相应的低聚硅基修饰的茂金属[（MeO）Si]SiMClCp（-）进行了选择性单取代。令人惊讶的是，用这种硅化物进行双硅化反应是不可能的。然而，在二氯钛茂的情况下，形成了稳定的自由基[（MeO）Si]SiTiCp（）。双硅化茂金属的分离失败促使我们研究另一种硅化物的反应活性。因此，我们合成了一种迄今未知的双硅化物K[（MeO）Si]Si（SiMe）Si[（MeO）Si]K（），其产率良好。化合物与不同的茂金属二氯化物（M = Ti、Zr和Hf）反应，以良好的产率生成了杂环化合物。
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