Heterogenization of molecular catalysts within porous solids: the case of Ni-catalyzed ethylene oligomerization from zeolites to metal-organic frameworks.

The last decade has seen a tremendous expansion of the field of heterogenized molecular catalysis, especially with the growing interest in metal-organic frameworks and related porous hybrid solids. With successful achievements in the transfer from molecular homogeneous catalysis to heterogenized processes come the necessary discussions on methodologies used and a critical assessment on the advantages of heterogenizing molecular catalysis. Here we use the example of nickel-catalyzed ethylene oligomerization, a reaction of both fundamental and applied interest, to review heterogenization methodologies of well-defined molecular catalysts within porous solids while addressing the biases in the comparison between original molecular systems and heterogenized counterparts.

Rhodium-Based Metal-Organic Polyhedra Assemblies for Selective CO Photoreduction.

Heterogenization of molecular catalysts via their immobilization within extended structures often results in a lowering of their catalytic properties due to a change in their coordination sphere. Metal-organic polyhedra (MOP) are an emerging class of well-defined hybrid compounds with a high number of accessible metal sites organized around an inner cavity, making them appealing candidates for catalytic applications. Here, we demonstrate a design strategy that enhances the catalytic properties of dirhodium paddlewheels heterogenized within MOP (Rh-MOP) and their three-dimensional assembled supramolecular structures, which proved to be very efficient catalysts for the selective photochemical reduction of carbon dioxide to formic acid.