The complexes [Ba{(C5Me5)(2)Ti2F7}(2)(hmpa)].(THF), 1.hmpa.(THF), and [BasTi(6)F(30)I(2)(C5Me5)(6)(hmpa)(6)][I-3](2).10(THF), 2[I-3](2).10(THF), were prepared from [Hdmpy](+)[(C5Me5)(2)Ti2F7](-) (dmpy = 2,6-dimethylpyridine), BaI2, and hmpa (hmpa = hexamethylphosphoramide). They were characterized by H-1 and F-19 NMR and IR spectroscopy and examined by single-crystal X-ray crystallography. The complexation equilibrium of the barium ion in 1 with hmpa and the dynamics of the barium ion moving on the fluorine surfaces Of [(C5Me5)(2)Ti2F7](-) in 1.hmpa have been studied by variable-temperature F-19 NMR spectroscopy. The core of the complex 2[I-3](2).10(THF) resembles the basic structural unit of the cubic perovskite.