化学
催化作用
催化循环
Atom(片上系统)
铜
光化学
氧化加成
氧化磷酸化
电子
结晶学
计算化学
有机化学
量子力学
物理
嵌入式系统
生物化学
计算机科学
作者
Guanglin Wang,Y. Liu,Xiangyu Zhang,Xupeng Zong,Xu Zhang,Kun Zheng,Dan Qu,Li An,Xiaotian Qi,Zaicheng Sun
摘要
Understanding the valency and structural variations of metal centers during reactions is important for mechanistic studies of single-atom catalysis, which could be beneficial for optimizing reactions and designing new protocols. Herein, we precisely developed a single-atom Cu(I)-N4 site catalyst via a photoinduced ligand exchange (PILE) strategy. The low-valent and electron-rich copper species could catalyze hydrophosphinylation via a novel single-electron oxidative addition (OA) pathway under light irradiation, which could considerably decrease the energy barrier compared with the well-known hydrogen atom transfer (HAT) and single electron transfer (SET) processes. The Cu(I)–Cu(II)–Cu(I) catalytic cycle, via single-electron oxidative addition and photoreduction, has been proven by multiple in situ or operando techniques. This catalytic system demonstrates high efficiency and requires room temperature conditions and no additives, which improves the turnover frequency (TOF) to 1507 h–1. In particular, this unique mechanism has broken through the substrate limitation and shows a broad scope for different electronic effects of alkenes and alkynes.
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