Reverse-Flow Adsorption for Process-Integrated Recycling of Homogeneous Transition-Metal Catalysts

Supramolecular strategies, based on hydrogen bonds and ionic interactions, were investigated as tools for the recovery and recycling of homogeneous transition‐metal catalysts by using reverse‐flow adsorption (RFA) technology. The association (in solution) and adsorption (on support) of new functionalized host materials and phosphine guest ligands, functionalized with the complementary binding motifs, were fine‐tuned for the application of these materials in a RFA reactor. The RFA technology for process‐integrated recycling of homogeneous catalysts using these tailor‐made phosphine ligands and silica‐supported host materials resulted in a stable, semicontinuous catalytic system. Rhodium‐catalyzed asymmetric hydrogenation of methyl acetamidoacrylate and asymmetric hydrosilylation of acetophenone were studied as test reactions. Depending on the catalytic process the metal complex could be recycled several times without significant loss in conversion. A supramolecular strategy based on hydrogen bonds and ionic interactions between tailor‐made phosphine ligand guests and silica‐supported host materials was used for integrated recycling of homogeneous transition‐metal catalysts in a reverse‐flow adsorption (RFA) process (see scheme), and resulted in a stable semicontinuous catalytic system. Depending on the catalytic process, the metal complex can be recycled several times without significant loss.