化学
配体(生物化学)
试剂
组合化学
螯合作用
胺气处理
反应性(心理学)
金属
氧化还原
光化学
有机化学
医学
生物化学
替代医学
受体
病理
作者
Nicholas G. Boekell,Caroline O. Bartulovich,Sandeepan Maity,Robert A. Flowers
出处
期刊:Inorganic Chemistry
[American Chemical Society]
日期:2023-03-13
卷期号:62 (12): 5040-5045
被引量:2
标识
DOI:10.1021/acs.inorgchem.3c00298
摘要
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 (SmBr2-NMEA) reagent system displayed the best combination of metal–ligand affinity and stability against H2 evolution. The use of SmBr2-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 SmBr2-water-amine system. Finally, the SmBr2-NMEA reagent system was found to reduce substrates analogous to key intermediates in the nitrogen fixation process. These results reveal SmBr2-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.
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