Synthesis of a Germylidenide Anion from the C–C Bond Activation of a Bis(germylene)

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• 作者：Celestine Seow ; Hong-Wei Xi ; Yongxin Li ; Cheuk-Wai So
• 刊名：Organometallics
• 出版年：2016
• 出版时间：April 25, 2016
• 年：2016
• 卷：35
• 期：8
• 页码：1060-1063
• 全文大小：246K
• 年卷期：0
• ISSN：1520-6041

文摘

The synthesis of a germylidenide anion by the C–C bond activation of a bis(germylene) is described. The reaction of the 2,6-bis(imino)phenyl bromide 1 with nBuLi, followed by reacting with GeCl₂·dioxane, afforded the chlorogermylene [LGeCl] (2, L = 2,6-(HCNtBu)₂C₆H₃). It was then reacted with 1 equiv of lithium in tetrahydrofuran (THF), which proceeded through the reduction of the imine skeleton, along with the C–C bond formation, to afford the bis(germylene) [2-(HC-NtBu)-6-(HC═NtBu)C₆H₃Ge:]₂ (3). It was further reacted with 2 equiv of lithium in THF, which proceeded through the reduction of the germanium(II) centers, followed by the homolytic cleavage of the C–C bond, to form the lithium germylidenide [LGeLi]₂ (4). Compounds 2–4 were characterized by NMR spectroscopy and X-ray crystallography. Their bonding natures were also investigated by theoretical studies.