Noncovalent Anchoring of Homogeneous Catalysts to Silica Supports with Well-Defined Binding Sites

Abstract

The efficient reversible functionalization of silica with catalytic sites using noncovalent interactions is described. We prepared silica materials with well-defined binding sites that selectively bind guest molecules that are equipped with the complementary binding motif, with the interaction between the two components being based on either hydrogen bonds or metal-ligand interactions. Several phosphine ligands functionalized with glycine-urea groups, required for hydrogen bond formation to the complementary host on the silica, have been prepared. The resulting noncovalently immobilized complexes have been used as a ligand system in the Pd-catalyzed allylic substitution and Rh-catalyzed hydroformylation of 1-octene. The supramolecular interaction between the transition-metal catalyst and the binding site located at the support is sufficiently strong to enable efficient catalyst recycling. In addition, the nature of the support facilitates the de- and refunctionalization of support, allowing the recycling of both homogeneous catalysts and the functionalized support. A rhodium catalyst based on a functionalized xantphos ligand was used in the hydroformylation of 1-octene in 11 consecutive reactions without showing catalyst deterioration or metal leaching.