Immobilized catalysts were prepared by mixing the ligand Cp', [C5Me4(n-propyl-Si(OEt)(3))], with RhCl3 center dot xH(2)O for subsequent reaction with silica Aerosil 200 (system A) or by copolymerization with TEOS (system B). Both systems were applied on olefin hydrogenation, showing high activity and robustness, allowing for many recycles (TON = 1.0 x 10(5) for system A and 2.0 x 10(4) for system B). The characterization techniques (IR-DRIFTS, C-13-CPMAS, and TEM) suggest a molecular nature for catalytic species. According to the deuteration experiment, a tetra-hapto-Cp'-Rh would be formed on the surface during the catalytic runs. (C) 2018 Elsevier Inc. All rights reserved.