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Unprecedented Reactivities of Highly Reactive Manganese(III)–Iodosylarene Porphyrins in Oxidation Reactions
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-11-13 , DOI: 10.1021/jacs.0c10159
Lina Zhang 1 , Yong-Min Lee 1 , Mian Guo 1 , Shunichi Fukuzumi 1 , Wonwoo Nam 1, 2
Affiliation  

We report that Mn(III)-iodosylarene porphyrins, [MnIII(Porp)(sArIO)]+, are capable of activating the C-H bonds of hydrocarbons, including unactivated alkanes such as cyclohexane, with unprecedented reactivities, such as a low kinetic isotope effect, a saturation behavior of reaction rates, and no electronic effect of porphyrin ligands on the reactivities of [MnIII(Porp)(sArIO)]+. In oxygen atom transfer (OAT) reactions, the sulfoxidation of para-X-substituted thioanisoles by [MnIII(Porp)(sArIO)]+ affords a very unusual behavior in the Hammett plot with the saturation behavior of reaction rates and no electronic effect of porphyrin ligands on reactivities. The reactivities and mechanisms of [MnIII(Porp)(sArIO)]+ are then compared with those of the corresponding MnIV(Porp)(O) complex. The present study reports the first example of highly reactive Mn(III)-iodosylarene porphyrins with unprecedented reactivities in C-H bond activation and OAT reactions.

中文翻译:

氧化反应中高反应性锰 (III)-碘代芳烃卟啉的前所未有的反应性

我们报告说,Mn(III)-碘代芳烃卟啉 [MnIII(Porp)(sArIO)]+ 能够激活烃的 CH 键,包括未活化的烷烃,如环己烷,具有前所未有的反应性,如低动力学同位素效应,反应速率的饱和行为,并且卟啉配体对 [MnIII(Porp)(sArIO)]+ 的反应性没有电子效应。在氧原子转移 (OAT) 反应中,[MnIII(Porp)(sArIO)]+ 对对位 X 取代的苯硫醚的亚砜化在哈米特图中提供了一种非常不寻常的行为,具有反应速率的饱和行为并且没有电子效应卟啉配体对反应的影响。然后将 [MnIII(Porp)(sArIO)]+ 的反应性和机制与相应的 MnIV(Porp)(O) 复合物进行比较。
更新日期:2020-11-13
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