The development of alternatives to phosphine-containing pincer ligands for homogeneous hydrogenation is described. Ligands of the "NNS" type and their Ru- and Co-complexes were synthesised, characterised, and successfully applied in chemoselective hydrogenations. Complexes of the type RuCl2(NNS)(PPh3) selectively hydrogenated unsaturated aldehydes, ketones and esters. Cobalt complexes CoCl2(NNS), in contrast, were precursors for nanoparticles which selectively hydrogenated olefins. Additionally, the Trost ligand was used for the first time in the asymmetric hydrogenation of ketones.