Preparation, Structure, and Reactivity of Discrete Branched Oligogermanes

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• 作者：Monika L. Amadoruge ; James A. Golen ; Arnold L. Rheingold ; Charles S. Weinert
• 刊名：Organometallics
• 出版年：2008
• 出版时间：May 12, 2008
• 年：2008
• 卷：27
• 期：9
• 页码：1979 - 1984
• 全文大小：232K
• 年卷期：v.27,no.9(May 12, 2008)
• ISSN：1520-6041

文摘

The hydrogermolysis reaction of PhGeH₃ serves in the synthesis of discrete branched oligogermanes. Treatment of PhGeH₃ with 3 equiv of the α-germyl nitriles R₃GeCH₂CN (R₃ = Ph₃ or Bu₂CH₂CH₂OEt), which are generated in situ from the corresponding amides R₃GeNMe₂ and CH₃CN, furnishes the tetragermanes PhGe(GePh₃)₃ and PhGe(GeBu₂CH₂CH₂OEt)₃ in excellent yield. The crystal structure of PhGe(GePh₃)₃ was determined. This compound is the first branched oligogermane to be structurally characterized. Reaction of the tetragermane PhGe(GeBu₂CH₂CH₂OEt)₃ with Buⁱ₂AlH generated the intermediate hydride PhGe(GeBu₂H)₃. Subsequent treatment of PhGe(GeBu₂H)₃ with the synthons R₂Ge(NMe₂)CH₂CH₂OEt (R = Bu, Et, Ph) in CH₃CN solution furnished the heptagermanes PhGe(GeBu₂GeR₂CH₂CH₂OEt)₃ (R = Bu, Et, Ph). The latter process also proceeds through the in situ formation of the α-germyl nitriles R₂Ge(CH₂CN)CH₂CH₂OEt.