Unusual nuclear exchange within a germanium-containing aromatic ring that results in germanium atom transfer

The delivery of single atoms is highly desirable for the straightforward synthesis of complex molecules, however this approach is limited by a lack of suitable atomic transfer reagents. Here, we report a germanium atom transfer reaction employing a germanium analogue of the phenyl anion. The reaction yields a germanium-substituted benzene, along with a germanium atom which can be transferred to other chemical species. The transfer of atomic germanium is demonstrated by the formation of well-defined germanium doped molecules. Furthermore, computational studies reveal that the reaction mechanism proceeds via the first example of an aromatic-to-aromatic nuclear germanium replacement reaction on the germabenzene ring. This unusual reaction pathway was further probed by the reaction of our aromatic germanium anion with a molecular silicon species, which selectively yielded the corresponding silicon-substituted benzene derivative. Controlled atomic delivery is a desirable synthetic process. Here a germanium-substituted phenyl anion is shown to act as a germanium atom transfer reagent and demonstrated by the preparation of well-defined molecular germanium species.

Automated summary

A germanium atom transfer reaction using a germanium analogue of the phenyl anion is reported, which yields a germanium-substituted benzene and allows for subsequent transfer of the germanium atom. Computational studies reveal a novel aromatic-to-aromatic nuclear germanium replacement reaction on the germabenzene ring.