New Directions for Frustrated Lewis Pair Chemistry

The range of Lewis acids and bases that effect FLP chemistry on a broadening range of substrates continues to expand, demonstrating the general utility of this paradigm. FLPs operate by two electron processes, either involving the action of an encounter complex on a substrate or via an electron transfer pathway via a frustrated radical pair. With a broadening range of substrates and catalysts, the utility of FLP-mediated reactions has broadened from hydrogenations to include a range of organic transformations, asymmetric syntheses, and polymerizations. The concept of FLPs has been applied to understand and develop new heterogeneous catalysts as well as new materials including metal organic framework FLPs and FLP-based polymers. The concerted action of a Lewis acid and base can activate H2 and other small molecules. Such frustrated Lewis pairs (FLPs) have garnered much attention and prompted many investigations into the activation of small molecules and catalysis. Although the nature, mechanism of action, and range of FLP systems continues to expand, this concept has also inspired ever-widening chemistry. Applications in hydrogenation and polymerization catalysis, as well as in synthetic chemistry, have provided selective processes and metal-free protocols. Heterogeneous FLP catalysts are emerging, and polymeric FLPs offer avenues to unique materials and strategies for sensing and carbon capture. The prospects for further impact of this remarkably simple reaction paradigm are considered. The concerted action of a Lewis acid and base can activate H2 and other small molecules. Such frustrated Lewis pairs (FLPs) have garnered much attention and prompted many investigations into the activation of small molecules and catalysis. Although the nature, mechanism of action, and range of FLP systems continues to expand, this concept has also inspired ever-widening chemistry. Applications in hydrogenation and polymerization catalysis, as well as in synthetic chemistry, have provided selective processes and metal-free protocols. Heterogeneous FLP catalysts are emerging, and polymeric FLPs offer avenues to unique materials and strategies for sensing and carbon capture. The prospects for further impact of this remarkably simple reaction paradigm are considered. 1,4-diazabicyclo[2.2.2]octane; employed as a Lewis base. a small molecule containing a diazo functionality that can be activated by an FLP. the extent to which one enantiomer is present compared to the other, a measure of purity for the preparation of chiral compounds. the proposed close association of a Lewis acid and base, held together by dispersion interactions. conventionally a Lewis acid and base combination that are prevented from forming a stable Lewis adduct, and which can react with a wide range of small molecules. There are now many examples showing that FLP reactivity can be accessed from acid–base equilibria or even systems that appear to be classical Lewis acid–base adducts. two radical species that are generated by the transfer of an electron from a Lewis base to a Lewis acid of an FLP; FRPs react with small molecules via one-electron processes. mesityl 2,4,6-trimethylphenyl, a bulky aryl group. a particular MOF developed by Matérials Institute Lavoisier featuring Cr-metal centers. metal organic framework, metal ions coordinated by organic linkers to form 1D, 2D, or 3D structures. employed as a Lewis base. 1,2,2,6,6-pentamethylpiperidine; employed as a Lewis base. general term for a range of pyridine-bridged bis(oxazoline) ligands. the tailoring of the steric properties of the Lewis acid or base to prevent quenching with specific molecules, often applied to preventing the stable interaction of water with a Lewis acid. 2,2,6,6-tetramethylpiperidine; employed as a Lewis base.