Line shape analysis of NMR spectra collected over a range of temperatures serves as a guide for the rearrangement of inner coordination-sphere atoms at a chiral, eight-coordinate, rhenium(V) polyhydride complex, ReH5(PPh3)2(sec-butyl amine). Line shape analysis is also used to determine the activation parameters ΔH‡, ΔS‡, and ΔG‡ for those atom rearrangements.