The hydrogermolysis reaction between a germanium hydride and a germanium amide, which occurs via the in situ formation of an a-germyl nitrile, has proven to be an effective tool for the synthesis of a diverse variety of organo-oligogermanium compounds. Recently, we have used this methodology for the synthesis of branched oligogermanes containing either four or five catenated germanium atoms that have the general formula (Ph3Ge)3GeX (X = Ph, H, F, Cl, Br, or I) or (R3Ge)4Ge (R = Me or Ph). These compounds exhibit enhanced s-delocalozation when compared to their corresponding linear analogues. We have also prepared the linear oligogermanes Ph3Ge(GePh2)2H, Ph3Ge(GePh2)3H, Ge5Ph12, and Ge6Ph14 by the hydrogermolysis reaction. During the course of these investigations it was discovered that only one of the two hydrogen atoms in the dihydrides H(GePh2)xH (x = 3 or 4) will react with a single equivalent of germanium amide R3GeNMe2 to yield the product R3Ge(GePh2)xH, which can subsequently be further functionalized at the remaining hydrogen atom. These species have been characterized using X-ray diffraction, NMR (1H, 13C, and 73Ge) and UV/visible spectroscopy, and also by cyclic and differential pulse voltammetry. The structural, spectroscopic, and electrochemical attributes of these oligogermanes will be discussed.

Long-chain linear and branched oligogermanes: Structural, spectroscopic, and electrochemical properties

246th National Meeting (2013)

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