A guided ion beam tandem mass spectrometer is used to examine the kinetic energy dependence of reactions of the third-row transition metal cation, Re+, with molecular hydrogen and its isotopologues. A flow tube ion source produces Re+ in its S-7(3) electronic ground state. Reaction with H-2, D-2, and HD forms Re H+(Re D+) in endothermic processes. Modeling of the endothermic reaction cross sections yields the 0 K bond dissociation energy of D-0(Re+-H)=2.29+/-0.07 eV (221+/-6 kJ/mol). The experimental thermochemistry is consistent with ab initio calculations, performed here and in the literature. Theory also provides the electronic structures of these species and is used to examine the reactive potential energy surfaces. Results from reactions with HD provide insight into the reaction mechanisms and indicate that the late metal ion, Re+, reacts largely via a statistical mechanism. This is consistent with the potential energy surfaces which locate a stable Re H-2(+)(B-5(2)) complex. Results for this third-row transition metal system are compared with the first-row congener (Mn+) and found to have much higher reactivity towards dihydrogen and stronger M+-H bonds. These differences can be attributed to efficient coupling among surfaces of different spin along with lanthanide contraction and relativistic effects. (C) 2004 American Institute of Physics.