Using the enzymatic mechanism of phosphoesterase as a template, we were able to modify a metal–organic framework such that the hydrolysis rates were 50 times faster than previously demonstrated with UiO-66.

As a C1 feedstock, CO 2 has the potential to be uniquely highly economical in both a chemical and a financial sense. In particular, the highly atom-economical acid-catalyzed cycloaddition of CO 2 to epoxides to yield cyclic organic carbonates (OCs), a functionality having many important industrial applications, is an attractive reaction for the utilization of CO 2 as a chemical feedstock. Metal-organic frameworks (MOFs) are promising candidates in catalysis as they are a class of crystalline, porous, and functional materials with remarkable properties including great surface area, high stability, open channels, and permanent porosity. MOFs structure tunability and their affinity for CO 2 , makes them great catalysts for the formation of OCs using CO 2 and epoxides. In this review, we examine MOF-based catalytic materials for the cycloaddition of carbon dioxide to epoxides. Catalysts are grouped based on the location of catalytic sites, i.e., at the struts, nodes, defect sites, or some combination thereof. Additionally, important features of each catalyst system are critically discussed.

The synthesis, structural characterization, and ethylene polymerization properties of two neutrally charged Ni(II) phenoxyiminato catalysts are compared and contrasted. Complex FI-SO2-Ni features a −SO2– group embedded in the ligand skeleton, whereas control FI-CH2-Ni has the −SO2– replaced by a −CH2– functionality. In comparison with FI-CH2-Ni, at 25 °C, FI-SO2-Ni is 18 times more active, produces polyethylene with 3.2 times greater M W and 1.5 times branch content, and is significantly more thermally stable. The FI-SO2-Ni-derived polymer is a hyperbranched polyethylene (148 branches 1000 C–1, M W = 3500g mol–1) versus that from FI-CH2-Ni (98 branches 1000 C–1, M W = 1100g mol–1). DFT calculations argue that the distinctive FI-SO2-Ni catalytic behavior versus that of FI-CH2-Ni is associated with nonnegligible OSO···Ni interactions involving the activated catalyst.