This study elucidates structures, activation barriers, and the gas-phase reactivity of cationic ruthenium transfer hydrogenation catalysts of the structural type [(eta(6)-cym)RuX(pympyr)](+). In these complexes, the central ruthenium(+II) ion is coordinated to an eta(6)-bound p-cymene (eta(6)-cym), a bidentate 2-R-4-(2-pyridinyl)pyrimidine ligand (pympyr) with R = NH2 or N(CH3)(2), and an anion X = I-, Br-, Cl-, or CF3SO3-. We present infrared multiple-photon dissociation (IR-MPD) spectra of precursors (before HCl loss) and of activated complexes (after HCl loss), which elucidates C-H activation as the key step in the activation mechanism. A resonant two-color IR-MPD scheme serves to record several otherwise dark bands and enhances the validity of spectral assignments. We show that collision-induced dissociation (CID)-derived activation energies of the [(eta(6)-cym)RuX(pympyr)](+) (R = N(CH3)(2)) complexes depend crucially on the anion X. The obtained activation energies for the HX loss correlate well with quantum chemical activation barriers and are in line with the HSAB concept. We further elucidate the reaction of the activated complexes with D-2 under single-collision conditions. Quantum mechanical simulations substantiate that the resulting species represent analogues for hydrido intermediates formed after abstraction of H+ and H- from isopropanol, as postulated for the catalytic cycle of transfer hydrogenation by us before.