Monovalent Germanium Radical Stabilized by a Phenalenyl Scaffold

A monovalent (Non-Gomberg type) germanium radical 1 stabilized by phenalenyl-based bidentate ligand was synthe-sized. Because of the high thermal stability originating from spin delocalization over the phenalenyl moiety, it was possi-ble to isolate compound 1 in crystalline form by sublimation at ca. 300 °C. ESR spectra, crystallographic analysis, theo-retical calculations, and reactivities with carbon radicals suggest that the spin of 1 is distributed on the phenalenyl moie-ty, while 1 behaves as a germanium-centered radical in its reactions with C2Cl6, PhSSPh, and p-benzoquinone to form Ge−E (E = Cl, S, O) bonds.