New Heterogeneous Rh-Containing Catalysts Immobilized on a Hybrid Organic–Inorganic Surface for Hydroformylation of Unsaturated Compounds

Anchoring Rh complexes to the surface of a silica polyamine composite, which has a poly(allylamine) covalently grafted to the surface of amorphous silica gel, yielded a material that proved to be an effective and novel heterogeneous catalyst for hydroformylation of unsaturated compounds. Surface amino groups of the material were modified with phosphines by covalent and ionic coupling. The modified materials were then treated with Rh(acac)(CO)2, giving the catalysts K-1 and K-2. Catalysts were characterized by solid-state NMR spectroscopy, IR spectroscopy, XPS, TEM, and elemental analysis. The activity and stability of K-1 and K-2 were then studied for the hydroformylation of selected unsaturated compounds. Hydroformylation of terminal double bonds occurred selectively in the presence of internal double bonds. Characterization of the catalysts and the problems encountered with the supported catalysts are discussed. Catalyst K-1 is reusable and can be applied to the hydroformylation of linear olefins, styrene, 4-vinylcyclohexene, and dienes, as well as representative terpenes and other unsaturated hydrocarbons in a batch reactor.