Preparation of Oligogermanes via the Hydrogermolysis Reaction
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- 作者：Esla Subashi ; Arnold L. Rheingold ; and Charles S. Weinert
- 刊名：Organometallics
- 出版年：2006
- 出版时间：June 19, 2006
- 年：2006
- 卷：25
- 期：13
- 页码：3211 - 3219
- 全文大小：173K
- 年卷期：v.25,no.13(June 19, 2006)
- ISSN：1520-6041
文摘
The hydrogermolysis reaction has been shown to be useful for the formation of germanium-germaniumbonds. The Ge-Ge bond forming reaction involves a germanium amide and a germanium hydride andrequires the use of acetonitrile as the solvent. A key factor in the formation of the Ge-Ge bond involvesreaction of the germanium amide R3GeNMe2 with acetonitrile solvent to furnish an 
chars/alpha.gif" BORDER=0>-germylated nitrileR3GeCH2CN which contains a labile Ge-C bond. This species undergoes subsequent reaction with agermanium hydride R3GeH to form the Ge-Ge bond. Using this method, the digermanes Bun3GeGePh3and Et3GeGePh3 have been obtained and their X-ray crystal structures have been determined. Thepreparation of three synthons for stepwise oligogermane chain buildup, R2Ge(NMe2)CH2CH2OEt (R =Et, Bu, Ph), has also been achieved. These synthons react with Ph3GeH in CH3CN to afford thecorresponding digermanes, which in the case of R = Et and Bu undergo subsequent reaction with DIBAL-Hto generate a digermane hydride. The ethyl and n-butyl digermane hydrides then are subsequently reactedwith an additional equivalent of the appropriate synthon to produce the corresponding trigermanes, andrepetition of these two steps furnishes the tetragermanes Ph3GeGe(R2)Ge(R2)Ge(R2)CH2CH2OEt (R =Et, Bu). Thus, in this study two new series of oligomeric organogermanium species have been preparedand fully characterized.
chars/alpha.gif" BORDER=0>-germylated nitrileR3GeCH2CN which contains a labile Ge-C bond. This species undergoes subsequent reaction with agermanium hydride R3GeH to form the Ge-Ge bond. Using this method, the digermanes Bun3GeGePh3and Et3GeGePh3 have been obtained and their X-ray crystal structures have been determined. Thepreparation of three synthons for stepwise oligogermane chain buildup, R2Ge(NMe2)CH2CH2OEt (R =Et, Bu, Ph), has also been achieved. These synthons react with Ph3GeH in CH3CN to afford thecorresponding digermanes, which in the case of R = Et and Bu undergo subsequent reaction with DIBAL-Hto generate a digermane hydride. The ethyl and n-butyl digermane hydrides then are subsequently reactedwith an additional equivalent of the appropriate synthon to produce the corresponding trigermanes, andrepetition of these two steps furnishes the tetragermanes Ph3GeGe(R2)Ge(R2)Ge(R2)CH2CH2OEt (R =Et, Bu). Thus, in this study two new series of oligomeric organogermanium species have been preparedand fully characterized.