The hydrogenation catalyst precursors $[(L-L)Rh(NBD)]ClO_4;(L-L=Fe({eta}^5-C_5H_4PBu^t;_2)_2,;Fe({eta}^5-C_5H_4PPhBu^t)_2$; NBD = norbornadiene) react with $H_2(1;atm,;30^{circ}C$, MeOH) to yield $[(L-L)HRh({mu}-H)_3RhH(L-L)]ClO_4$. These hydrido species are fluxional, and variable temperature NMR studies show the existence of a number of equilibria involving both fluxional and non-fluxional species. The synthesis, solution structures, and fluxional behaviors of these hydrides are described.