Synthesis of Alkoxy‐Substituted Oligosilanes using [β‐(Alkoxy)disilanyl]lithium

• Published in: European journal of inorganic chemistry 2021-10, Vol.2021 (39), p.4096-4102
• Main Authors: Matsuo, Takumi, Yamaguchi, Tatsuya, Hirohata, Tomoki, Nakamoto, Masaaki, Yamamoto, Yohsuke, Maeda, Yutaka, Kawachi, Atsushi
• Format: Article
• Language: English
• Subjects: Alkoxy group; Conjugation; Crystallography; Density functional theory; Functional groups; Inorganic chemistry; Lithium; Mass spectrometry; NMR spectroscopy; Reduction; Silane; Silyl anion; Synthesis; Tin-lithium exchange
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.202100668

Herein, the synthesis of (tert‐butoxy)oligosilanes using [β‐(tert‐butoxy)disilanyl]lithium 3 is described. Compound 3 was prepared by (a) the reduction of (tert‐butoxy)chlorodiphenylsilane (1) with lithium and (b) tin‐lithium exchange of [(tert‐butoxy)diphenylsilyl]stannane 6 with n‐BuLi. Disilanyllithium 3 was reacted with mono‐ and dihalosilanes and a dihalodisilane to form tri‐, penta‐, and hexasilanes bearing tert‐butoxy groups at the terminal silicon atoms. Functional group transformations of the oligosilanes were also performed. The structures of the oligosilanes were characterized using nuclear magnetic resonance spectroscopy, ultraviolet‐visible spectroscopy, mass spectrometry, and X‐ray crystallography. The structures and photophysical properties were discussed based on density functional theory calculations. We present the synthesis of (tert‐butoxy)oligosilanes using [β‐(tert‐butoxy)disilanyl]lithium, which was prepared by (a) the reduction of (tert‐butoxy)chlorodiphenylsilane with lithium and (b) tin‐lithium exchange of [(tert‐butoxy)diphenylsilyl]stannane with n‐BuLi. Functional group transformations of the obtained oligosilanes were successful to form hydro‐, fluoro‐, and chloro‐substituted oligosilanes.