Search

Germaaluminocenes are formed by salt metathesis reactions of dipotassium germacyclopentadienediides with pentamethylcyclopentadienylaluminum dichloride. The reactivity pattern of these sandwich complexes is determined by the electrophilic central aluminum atom and by the nucleophilic dicoordinated germanium center. Surprisingly, the products formed by reactions with Lewis acids, Lewis bases, amphiphiles and compounds with polar double bonds are those expected from the reaction of a hypothetical aluminagermapentafulvene with these types of reagents. This suggests that germaaluminocenes are synthetic equivalents to these pentafulvenes., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The salt metathesis reaction of dipotassium germacyclopentadienediide with aluminum(III) dichlorides provides either half-sandwich alumole complexes of germanium(II) or aluminylene germole complexes. Their molecular structure and the delocalized bonding situation, revealed by density functional theory (DFT) calculations, are equally described as isomeric aluminagerma[5]pyramidanes with either the germanium or the aluminum atom in the apical position of the pentagonal pyramid. The product formation and the selectivity of the reaction depends on the third substituent of the aluminum dichloride. Aryl-substituents favor the formation of alumole complexes and Cp*-substituents that of the isomeric germole complexes. With amino-substituents at the aluminum atom mixtures of both isomers are formed and the positional exchange of the two heteroatoms is shown by NMR spectroscopy. The alumole complexes of germanium(II) undergo facile reductive elimination of germanium and form the corresponding alumoles., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The synthesis of two η 5 -aminoborole complexes of germanium(II) from the reaction of a germole dianion with aminoboron dichlorides is reported. This reaction constitutes a remarkable example of a germole-to-borole transformation. The two aminoborole complexes of germanium(II) were fully characterized by multinuclear NMR spectroscopy, IR spectroscopy, HRMS, and, in one case, by X-ray crystallography. The results of quantum-mechanical calculations favor the electronic structure of a half-sandwich complex of Ge II over an ionic representation with a germanium dication stabilized by an aromatic aminoborole dianion., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)