A Manganese Compound I Model with a High Reactivity in the Oxidation of Organic Substrates and Water
A Manganese Compound I Model with a High Reactivity in the Oxidation of Organic Substrates and Water
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DOI：
10.1021/jacs.3c01818
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发表时间：
2023-04-10
影响因子：
15
通讯作者：
Nam，Wonwoo
中科院分区：
文献类型：
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作者：
Zhang，Lina;Seo，Mi Sook;Nam，Wonwoo
合成了一种高价锰(IV)-羟基卟啉π-阳离子自由基配合物[Mn(IV)(OH)（Porp+•）(X)]+，并对其进行了光谱表征。锰卟啉中间体在烷烃羟基化反应和氧原子转移反应中具有较高的反应活性。更重要的是，锰卟啉中间体与水反应速度快，导致出氧。据我们所知，我们报道了第一个含有卟啉π-阳离子自由基配体的锰Cpd I模型化合物，该化合物在氧化反应中具有很高的反应活性，包括水氧化。
A high-valent manganese(IV)-hydroxo porphyrin π-cation radical complex, [Mn(IV)(OH)(Porp+•)(X)]+, was synthesized and characterized spectroscopically. The Mn porphyrin intermediate was highly reactive in alkane hydroxylation and oxygen atom transfer reactions. More importantly, the Mn porphyrin intermediate reacted with water at a fast rate, resulting in the dioxygen evolution. To the best of our knowledge, we report the first manganese Cpd I model compound bearing a porphyrin π-cation radical ligand with a high reactivity in oxidation reactions, including water oxidation.