The fluorine-substituted branched oligogermane (Ph 3 Ge) 3 GeF was successfully synthesized from (Ph 3 Ge) 3 GeH and [Ph 3 C][BF 4 ] after several unfruitful attempts using other synthetic methods and was formed as a mixture with Ph 3 GeF. Pure (Ph 3 Ge) 3 GeF could be obtained from the reaction mixture by successive recrystallizations and was characterized by elemental analysis and NMR ( 1 H, 13 C, and 19 F) spectroscopy, including a variable-temperature 19 F NMR study to investigate the presence or absence of hydrogen bonding in this species. The oligogermane (Ph 3 Ge) 3 GeF is indefinitely stable in the solid state under an inert atmosphere, but gradually decomposes to Ph 3 GeF and other unidentified products in solution. The X-ray crystal structure of (Ph 3 Ge) 3 GeF was obtained and represents the only crystallographically characterized germanium−fluorine compound having unsupported Ge−Ge bonds. The Ge 4 framework of the oligogermane (Ph 3 Ge) 3 GeF is isostructural with the other previously prepared halogen-substituted analogues (Ph 3 Ge) 3 GeX (X = Cl, Br, I). The position of the fluorine atom in the structure of (Ph 3 Ge) 3 GeF is disordered by displacement of a chlorine atom 39% of the time. The UV/visible spectrum and the cyclic and differential pulse voltammograms of (Ph 3 Ge) 3 GeF were obtained, and the relative energies of the frontier orbitals were determined using DFT computations.

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