Metal aryloxide complexes are known for the majority of main group and transition metals. However, aryloxide complexes of germanium are uncommon, especially when germanium is in the +2 oxidation state. Both monomeric and dimeric complexes containing simple aryloxide ligands are known, and some germanium aryloxides containing calix[n]arene or binaphthoxide ligands, as well as cluster-type materials, have also been reported. The aryloxides are synthesized by the protonolysis reaction between a bulky germanium (II) amide and the substituted phenol. Using this method, we have prepared several germanium (II) aryloxide and calix[n]arene complexes, including the minor calix[5]arene complex which is dimeric in the solid state (Figure). The germylenes Ge[N(SiMe3)2]2 and Ge[N(SiMe2Ph)2]2 have been used as starting materials and the identity of the amide ligands affect the outcome of the reactions. The germanium (II) calix[n]arene complexes have been characterized by 1H NMR spectroscopy, which reveals that the macrocyclic frameworks are rigid in solution. The NMR spectra have also been correlated with the X-ray structures of these compounds.

Synthesis and characterization of germanium (II) calixarenes and binaphthols

246th National Meeting (2013)

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