Palladium complexes with the chiral triaza ligands N,N'-bis{[(S)-(1-benzylpyrrolidin-2-yl)]methy}amine and N,N'-bis{[(S)-(1-benzylpyrrolidin-2-yl)]methyl}-N-propylamine have been obtained. The fixation of the preformed palladium complex, ([Pd(N,N'-bis{[(S)-(1-benzylpyrrolidin-2-yl)lmethyl)-N-[3-(triethoxysily l)propyl]amine)(cod)]PF6}, on mesostructured silicates and delaminated zeolites (silica, MCM-41, ITQ-2 and ITQ-6) and their use, under heterogeneous conditions, for the hydrogenation reactions are reported. The catalytic activity and selectivity are higher to that observed under homogeneous conditions, as a consequence of the complex- and/or reagents-to-support interaction. The strength of stable covalent bond between support and supported complex allows the recovery and recycling of the supported catalysts for a number of cycles. Atomic absorption analysis of the reaction solutions shows that there is no metal leaching into the solutions. A comparative catalytic study with the respective Rh(I) and Ir(I) complexes for olefin hydrogenation reactions was also given. (c) 2005 Elsevier B.V. All rights reserved.