Facile Synthesis of an Octagermacubane with Two Three‐Coordinate Germanium(0) Atoms and its Unique Radical Anion

Thermolysis of a 1 : mixture tris(di-tert-butylmethylsilyl)germane 9 and bis(di-tert-butylmethylsilyl)germane 17 at 100 °C produces unexpectedly octagermacubane 18, having two 3-coordinate Ge0 atoms (40 % yield). 18 was characterized by X-ray crystallography it is singlet biradical (according to DFT quantum mechanical calculations the absence an EPR signal). Reactions with CH2Cl2 H2O yield novel dichloro-octagermacubane 24 hydroxy-octagermacubane 25, respectively. Reduction tBuMe2SiNa in THF isolable radical anion 26-Na. Based on crystallography, spectroscopy calculations, 26-Na classified as Ge-centered anion.