In the presence of chlorinated solvents, the catalytic complex [Ir(COD)py(PCy3)]PF6 (where COD is 1,5-cyclooctadiene and py is pyridine) was an active catalyst for the hydrogenation of synthetic cis-1,4-polyisoprene and natural rubber. Detailed kinetic and mechanistic studies for homogeneous hydrogenation were carried out through the monitoring of the amount of hydrogen consumed during the reaction. The final degree of olefin conversion, measured with a computer-controlled gas-uptake apparatus, was confirmed by Fourier transform infrared spectroscopy and H-1-NMR spectroscopy. Synthetic cis-1,4-polyisoprene was used as a model polymer for natural rubber without impurities to Study the influence of the catalyst loading, polymer concentration, hydrogen pressure, and reaction temperature with a statistical design framework. The kinetic results for the hydrogenation of both synthetic cis-1,4-polyisoprene and natural rubber indicated that the hydrogenation rate exhibited a first-order dependence on the catalyst concentration and hydrogen pressure. Because of impurities inside the natural rubber, the hydrogenation of natural rubber showed an inverse behavior dependence on the rubber concentration, whereas the hydrogenation rate of synthetic rubber, that is, cis-1,4-polyisoprene, remained constant when the rubber concentration increased. The hydrogenation rate was also dependent on the reaction temperature. The apparent activation energies for the hydrogenation of synthetic cis-1,4-polyisoprene and natural rubber were evaluated to be 79.8 and 75.6 kJ/mol, respectively. The mechanistic aspects of these catalytic processes were discussed on the basis of observed kinetic results. The addition of some acids showed an effect on the hydrogenation rate of both rubbers. The thermal properties of hydrogenated rubber samples were determined and indicated that hydrogenation increased the thermal stability of the hydrogenated rubber but did not affect the inherent glass-transition temperature. (c) 2006 Wiley Periodicals, Inc.