A series of hydrogen rich Mg6–7TMH14–16 (TM = Ti, Zr, Hf, V, Nb and Ta) hydrides have been synthesized at 600 degree C in a high pressure anvil cell above 4 GPa. All have structures based on a fluorite type metal atom subcell lattice with a 4.8 . The TM atom arrangements are, however, more ordered and can best be described by a superstructure where the 4.8 FCC unit cell axis is doubled. The full metal atom structure corresponds to the Ca7Ge type structure. This superstructure was also observed from electron diffraction patterns. The hydrogen atoms were found from powder X-ray diffraction using synchrotron radiation to be located in the two possible tetrahedral sites. One coordinates three Mg atoms and one TM atom and another coordinates four Mg atoms. These types of new hydrogen rich hydrides based on immiscible metals were initially considered as metastable but have been observed to be reversible if not fully dehydrogenated. In this work, DFT calculations suggest a mechanism whereby this can be explained: with H more strongly bonded to the TM, it is in principle possible to stepwise dehydrogenate the hydride. The remaining hydrogen in the tetrahedral site coordinating the TM would then act to prevent the metals from separating, thus making the system partially reversible.