Synthesis and Characterization of Methoxylated Oligosilyl Group 4 Metallocenes

Aileen Sauermoser; Thomas Lainer; Gabriel Glotz; Frank Czerny; Bettina Schweda; Roland C Fischer; Michael Haas

doi:10.1021/acs.inorgchem.2c02112

Synthesis and Characterization of Methoxylated Oligosilyl Group 4 Metallocenes

Inorg Chem. 2022 Sep 19;61(37):14742-14751. doi: 10.1021/acs.inorgchem.2c02112. Epub 2022 Sep 1.

Authors

Aileen Sauermoser¹, Thomas Lainer¹, Gabriel Glotz², Frank Czerny³, Bettina Schweda⁴, Roland C Fischer¹, Michael Haas¹

Affiliations

¹ Institute of Inorganic Chemistry, Graz University of Technology, Stremayrgasse 9/V, A-8010 Graz, Austria.
² Institute of Physical and Theoretical Chemistry, Graz University of Technology, Stremayrgasse 9/II, 8010 Graz, Austria.
³ Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, 10623 Berlin, Germany.
⁴ Institute for Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9/IV, A-8010 Graz, Austria.

Abstract

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.