A novel type of metastable complexes of metal (such as Na) atoms with a super-fluorinated carbon molecule is investigated, with a carbon atom exhibiting a unique, pentavalent character. It is induced by the charge transfer from the alkali metal component, followed by a geometric compression of the ion pair system. Analysis of the electron-density distribution confirms the real chemical nature of the extra C-F bond. Structure and stability of the system are characterized ab initio, and a spectrum of electronic perturbations is considered. The ways of forming the systems are discussed, and the spectroscopic parameters are predicted, facilitating their detection in experiments.