Time-resolved X-ray absorption spectroscopy (TR-XAS) has so far practically been limited to large-scale facilities, to sub-picosecond temporal resolution and to the condensed phase. Here, we report the realization of TR-XAS with a temporal resolution in the low femtosecond range by developing a table-top high-harmonic source reaching up to 350 eV, thus partially covering the spectral region of 280 to 530 eV, where water is transmissive. We use this source to follow previously unexamined light-induced chemical reactions in the lowest electronic states of isolated CF+4 and SF+6molecules in the gas phase. By probing element-specific core-to-valence transitions at the carbon K-edge or the sulfur L-edges, we characterize their reaction paths and observe the effect of symmetry breaking through the splitting of absorption bands and Rydbergvalence mixing induced by the geometry changes.