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Updated: Apr 14, 2026

Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups
Published on: February 11, 2012
Intermolecular Electrophilic Germylation Using GeCl4 and Al2Cl6
Justyna Łosiewicz1, Milan Kumar Bisai1, Zachary A Bub1
1EaStCHEM School of Chemistry, University of Edinburgh, Edinburgh, UK.
Abstract:
Electrophilic aromatic substitution is a textbook transformation for the lighter Group 14 elements. In contrast to acylation, alkylation, and silylation, electrophilic germylation is extremely underdeveloped. Herein we report the first effective intermolecular Germa-Friedel-Crafts reaction. Specifically, combining the key industrial precursor GeCl4, with Al2Cl6 and an inexpensive hindered pyridine base enables electrophilic C-H germylation of a range of arenes. The process can be applied for selective synthesis of either the mono- or the di-aryl germanes, ArGeCl3 and Ar2GeCl2, respectively. ArGeCl3 are versatile intermediates that can be transformed in situ into the synthetically desirable ArGe(alkyl)3 derivatives. Mechanistic and computational analysis support an SEAr-type process where Al2Cl6 is the key halophilic activator that generates a germanium electrophile able to effect C-H germylation in combination with the base. Overall, this work demonstrates that a high-yielding intermolecular Germa-Friedel-Crafts reaction is possible provided an appropriate Brønsted base is used.
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