长寿命 N-氧自由基的生成与束缚及其光催化作用。
Generation and Confinement of Long-Lived N-Oxyl Radical and Its Photocatalysis.
机构信息
State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics , Dalian 116023, China.
University of Chinese Academy of Sciences , Beijing 100049, China.
出版信息
J Am Chem Soc. 2018 Feb 14;140(6):2032-2035. doi: 10.1021/jacs.7b12928. Epub 2018 Feb 1.
Generation of controllable carbon radical under the assistance of N-oxyl radical is an efficient method for the activation of C-H bonds in hydrocarbons. We herein report that irradiation of α-FeO and N-hydroxyphthalimide (NHPI) under 455 nm light generates phthalimide-N-oxyl radical (PINO*), which after being formed by oxidation with holes, is confined on α-FeO surface. The half-life time of the confined radical reaches 22 s as measured by in situ electron paramagnetic resonance (EPR) after the light being turned off. This allows the long-lived N-oxyl radical to abstract the H from C-H bond to form a carbon radical that reacts with molecular oxygen to form RC-OO· species, decomposition of which leads to oxygenated products.
在氮氧自由基的辅助下生成可控碳自由基是一种有效激活碳氢化合物中 C-H 键的方法。我们在此报告，在 455nm 光的照射下，α-FeO 和 N-羟基邻苯二甲酰亚胺（NHPI）会产生邻苯二甲酰亚胺-N-氧自由基（PINO*），其在空穴氧化后形成，并局限在α-FeO 表面上。通过关闭光后的原位电子顺磁共振（EPR）测量，封闭自由基的半衰期达到 22 秒。这使得长寿命的氮氧自由基能够从 C-H 键中提取 H 形成碳自由基，该自由基与分子氧反应形成 RC-OO·物种，其分解导致含氧产物的形成。
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