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

Aileen Sauermoser, Thomas Lainer, Gabriel Glotz, Frank Czerny, Bettina Schweda, Roland C. Fischer, Michael Haas^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	14742-14751
Number of pages	10
Journal	Inorganic Chemistry
Volume	61
Issue number	37
DOIs	https://doi.org/10.1021/acs.inorgchem.2c02112
Publication status	Published - 19 Sept 2022

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.2c02112Licence: CC BY 4.0

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title = "Synthesis and Characterization of Methoxylated Oligosilyl Group 4 Metallocenes",

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.",

author = "Aileen Sauermoser and Thomas Lainer and Gabriel Glotz and Frank Czerny and Bettina Schweda and Fischer, {Roland C.} and Michael Haas",

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AU - Sauermoser, Aileen

AU - Lainer, Thomas

AU - Glotz, Gabriel

AU - Czerny, Frank

AU - Schweda, Bettina

AU - Fischer, Roland C.

AU - Haas, Michael

PY - 2022/9/19

Y1 - 2022/9/19

N2 - 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.

AB - 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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Synthesis and Characterization of Methoxylated Oligosilyl Group 4 Metallocenes

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