A series of ruthenium(II) complexes have been prepared by using bidentate chelating N-heterocyclic carbene (NHC) ligands that feature different donor groups E (E = olefin, thioether, carboxylate, and NHC). Rigid coordination of all donor sites was concluded from NMR spectroscopy, and the electronic impact of the donor group was evaluated by electrochemical analyses. The chelating donor group had a strong influence on the activity of the metal center in catalyzing direct hydrogenation of styrene. A thioether group or a second NHC donor site essentially deactivates the metal center. Complexes comprising a NHC tethered with an olefin or a carboxylate group showed appreciable activity, though only the carboxylate-functionalized system proved to be a precursor for homogeneous hydrogenation. According to in situ high-pressure NMR analyses, complexes featuring a carboxylate chelating group are remarkably resistant toward reductive elimination even under strongly reducing conditions and may, therefore, be used repeatedly.