Accessing Unusual Reactivity through Chelation-Promoted Bond Weakening.

Highly reducing Sm(II) reductants and protic ligands were used as a platform to ascertain the relationship between low-valent metal-protic ligand affinity and degree of ligand X-H bond weakening with the goal of forming potent proton-coupled electron transfer (PCET) reductants. Among the Sm(II)-protic ligand reductant systems investigated, the samarium dibromide N -methylethanolamine (SmBr 2 -NMEA) reagent system displayed the best combination of metal-ligand affinity and stability against H 2 evolution. The use of SmBr 2 -NMEA afforded the reduction of a range of substrates that are typically recalcitrant to single-electron reduction including alkynes, lactones, and arenes as stable as biphenyl. Moreover, the unique role of NMEA as a chelating ligand for Sm(II) was demonstrated by the reductive cyclization of unactivated esters bearing pendant olefins in contrast to the SmBr 2 -water-amine system. Finally, the SmBr 2 -NMEA reagent system was found to reduce substrates analogous to key intermediates in the nitrogen fixation process. These results reveal SmBr 2 -NMEA to be a powerful reductant for a wide range of challenging substrates and demonstrate the potential for the rational design of PCET reagents with exceptionally weak X-H bonds.