The catalytic hydrogenation of cyclohexene and 1-methylcydohexene is investigated experimentally and by means of density functional theory (DFT) computations using novel ruthenium Xantphos(Ph) (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) and Xantphos(Cy) (4,5-bis-(dicydohexylphosphino)-9,9-dimethylxanthene) precatalysts [Ru(XantphosPh)(PhCO2)(Cl)] (1) and [Ru(Xantphos(Cy))-(PhCO2)(Cl)] (2), the synthesis, characterization, and crystal structures of which are reported. The intention of this work is to (i) understand the reaction mechanisms on the microscopic level and (ii) compare experimentally observed activation barriers with computed barriers. The Gibbs free activation energy Delta G(double dagger) was obtained experimentally with precatalyst 1 from Eyring plots for the hydrogenation of cydohexene (Delta G(double dagger) = 17.2 + 1.0 kcal/ mol) and 1-methylcydohexene (Delta G(double dagger) = 18.8 +/- 2.4 kcal/mol), while the Gibbs free activation energy Delta G(double dagger) for the hydrogenation of cyclohexene with precatalyst 2 was determined to be 21.1 +/- 2.3 kcal/mol. Plausible activation pathways and catalytic cycles were computed in the gas phase (M06-L/def2-SVP). A variety of popular density functionals (omega 397X-D, LC-omega PBE, CAM-B3LYP, B3LYP, B97-D3BJ, B3LYP-D3, BP86-D3, PBEO-D3, M06-L, MN12-L) were used to reoptimize the turnover determining states in the solvent phase (DF/def2-TZVP: IEF-PCM and/or SMD) to investigate how well the experimentally obtained activation barriers can be reproduced by the calculations. The density functionals B97-D3BJ, MN12-L, M06-L, B3LYPD3, and CAM-B3LYP reproduce the experimentally observed activation barriers for both olefins very well with very small (0.1 kcal/mol) to moderate (3.0 kcal/mol) mean deviations from the experimental values indicating for the field of hydrogenation catalysis most of these functionals to be useful for in silico catalyst design prior to experimental work.