The water soluble pyridyl-triazole ligand sodium 2-(1-((pyridin-2-yl)methyl)-1H-1,2,3-triazol-4-yl) ethyl sulfate (Nal) has been successfully employed in combination with ruthenium and iridium for catalytic hydrogenation of C=C and C=O double bonds in water/toluene biphasic systems. Reaction of the ligand with [RuCl2(eta(6)-p-cymene)](2) affords the new water soluble complex [RuCl(eta(6)-p-cymene)(1)] (2) which has been found to be catalytically active in the water/organic solvent biphasic hydrogenation using styrene and 2-cyclohexen-1-one as model substrates. Very conveniently, the iridium based catalytic system is prepared by simply stirring in water [Ir(eta(4)-COD)C1]2 with Nal (Ir:Nal molar ratio-1:4), the resulting solution is catalytically active and appears more efficient than 2. With both the Ru- and Ir-based systems the catalytically active aqueous phases can be used at least three times without loss of activity. (C) 2014 Elsevier B.V. All rights reserved.