New mononuclear ruthenium complexes with general formula [Ru(bid)(B)(Cl)] (bid is (1Z,3Z)-1,3-bis(pyridin-2-ylmethylene)isoindolin-2-ide; B = bidentate ligand 2,2′-bipyridine or R₂–bpy, where R = COOEt or OMe) were synthesized and tested as precatalysts for the hydrogenative reduction of CO₂ in 2,2,2-trifluoroethanol (TFE) as solvent with added NEt₃. Significant amounts of formic acid were produced by these catalysts and a kinetic analysis based on initial rate constants was carried out. The potential mechanisms including intermediate species for these catalytic systems were investigated by means of quantum chemical calculations to gain deeper insight into the processes. The effect of electron-donating and electron-withdrawing groups on catalyst performance was studied both experimentally and theoretically.