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Radiation-induced aerobic oxidation via solvent-derived peroxyl radicals

机译:通过溶剂衍生的过氧自由基进行辐射诱导的有氧氧化

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摘要

Oxidation is a fundamental transformation in synthesis. Developing facile and effective aerobic oxidation processes under ambient conditions is always in high demand. Benefiting from its high energy and good penetrability, ionizing radiation can readily produce various reactive species to trigger chemical reactions, offering another option for synthesis. Here, we report an ionizing radiation-induced aerobic oxidation strategy to synthesize oxygen-containing compounds. We discovered that molecular oxygen (O2) could be activated by reactive particles generated from solvent radiolysis to produce solvent-derived peroxyl radicals (RsolOO·), which facilitated the selective oxidation of sulfides and phosphorus(iii) compounds at room temperature without catalysts. Density functional theory (DFT) calculations further revealed that multiple RsolOO· enable the oxidation reaction through an oxygen atom transfer process. This aerobic oxidation strategy broadens the research scope of radiation-induced chemical transformations while offering an opportunity to convert nuclear energy into chemical energy.
机译:氧化是合成中的一个基本转变。在环境条件下开发简单有效的有氧氧化工艺的需求一直很高。得益于其高能量和良好的穿透性,电离辐射可以很容易地产生各种反应性物质来触发化学反应,为合成提供了另一种选择。在这里,我们报道了一种电离辐射诱导的有氧氧化策略来合成含氧化合物。我们发现分子氧 (O2) 可以被溶剂辐射分解产生的反应颗粒激活,产生溶剂衍生的过氧自由基 (RsolOO·),这有利于在室温下无需催化剂即可实现硫化物和磷 (iii) 化合物的选择性氧化。密度泛函理论 (DFT) 计算进一步表明,多个 RsolOO·通过氧原子转移过程实现氧化反应。这种好氧氧化策略拓宽了辐射诱导化学转化的研究范围,同时提供了将核能转化为化学能的机会。

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