Mono- and bimetallic Rh and Rh-Co complexes containing oligoallene ligands were synthesized. Their catalytic activity was examined in the hydrogenation of unsaturated compounds, such as isoprene, hexene-1, and toluene. The catalytic activity of Rh(DMA)(ol) and Rh-Co(DMA)(ol) was shown to be 16 800 and 23000 mol/(mol h) in the hydrogenation of hexene-1 and 72 and 90 mol/(mol h) in the hydrogenation of toluene, respectively. Isoprene is hydrogenated completely: the rate curves exhibit two portions corresponding to hydrogenation of both double bonds. The catalytic activity of palladium oligodimethylallene complexes deposited on an inorganic support (gamma-Al(2)O(3)) in isoprene hydrogenation depends on the support preparation procedure, the particle size, and the metal loading on the surface. Heterogenization of the homogeneous mono- and bimetallic Rh and Pd complexes somewhat enhances the catalytic activity in hydrogenation of the given substrates.