Selective Synthesis and Derivatization of Germasilicon Hydrides

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• 作者：Harald Stueger ; Viktor Christopoulos ; Andrea Temmel ; Michael Haas ; Roland Fischer ; Ana Torvisco ; Odo Wunnicke ; Stephan Traut ; Susanne Martens
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：April 18, 2016
• 年：2016
• 卷：55
• 期：8
• 页码：4034-4038
• 全文大小：300K
• 年卷期：0
• ISSN：1520-510X

文摘

Mixed Si/Ge hydrides Si_xGe_yH_z are valuable precursors for the deposition of binary Si–Ge alloys. This work describes the synthesis and full characterization of the previously unknown germaisotetrasilane Ph₃GeSi(SiH₃)₃ (2) on a multigram scale from the reaction of the lithium silanide LiSi(SiH₃)₃ with Ph₃GeCl. The stability of the Si–Ge bond in 2 versus electrophiles and nucleophiles has been investigated with the primary aim of developing new approaches to mixed sila-H-germanes (H₃Ge)_xSi(SiH₃)_4–x. With 1 equiv of MeLi, 2 reacted cleanly under cleavage of one Si–Si bond to give Ph₃GeSi(SiH₃)₂Li, which is a valuable synthon for further derivatization. In contrast, the dephenylation reaction of 2 with 1 or 2 equiv of CF₃SO₃H/iBu₂AlH proceeded much less selectively and afforded the desired Ph/H-germasilanes Ph₂HGeSi(SiH₃)₃ and PhH₂GeSi(SiH₃)₃ along with considerable amounts of Si–Ge scission products.