A sol-gel entrapped 1:3 mixture of [ Rh(cod)Cl](2) and Na[HRu3(CO)(11)] catalyzes the hydrogenation of various unsaturated substrates by two distinguishable mechanisms. Under 13.8 bar H-2 and 20 degrees C methylated arenes react rapidly to give cycloalkane derivatives. XRD and TEM studies showed that under these conditions the hydrogenation proceeds without the generation of free metal particles. The hydrogenation of non-methylated arenes, as well as that of alkenes and alkynes, require a temperature of 80-120 degrees C at which the entrapped complexes form metallic nano-particles of 3-5 nm. Chloroarenes are also hydrodechlorinated at 120 degrees C, but require a hydrogen pressure of >= 25 bar. At both temperature ranges the catalysts are reusable at least four times. The high efficiency of the hydrogenation process at 20 degrees C is rationalized by a synergistic effect between the two different metal atoms of the combined catalyst. This may be related to a remote control model through a hydrogen spillover mechanism. (C) 2008 Elsevier B.V. All rights reserved.