Stable Diporphyrinylaminyl Radical and Nitrenium Ion.
Stable Diporphyrinylaminyl Radical and Nitrenium Ion.
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DOI：
10.1002/anie.201805385
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发表时间：
2018-06
影响因子：
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通讯作者：
Daiki Shimizu;Keisuke Fujimoto;A. Osuka
中科院分区：
文献类型：
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作者：
Daiki Shimizu;Keisuke Fujimoto;A. Osuka
氮正离子是卡宾的等电子氮对应物，是各种生物和化学过程的重要中间体。在这里，我们描述了第一个合成和表征的一个稳定的nitrenium离子没有共振稳定相邻的氨基。即，通过稳定的氨基自由基逐步氧化相应的二卟啉胺，合成了二卟啉基氮鎓离子的稳定盐。氮鎓离子表现出诸如单重基态、中心C-N键的增强的双键特征、对水和甲醇没有反应性以及负溶剂化变色行为的特征。
Nitrenium ions, isoelectronic nitrogen counterparts of carbenes, are important intermediates in various biological and chemical processes. Herein we describe the first synthesis and characterization of a stable nitrenium ion without resonance stabilization by adjoining amino groups. Namely, a stable salt of a diporphyrinylnitrenium ion was synthesized by stepwise oxidation of the corresponding diporphyrinylamine through a stable aminyl radical. The nitrenium ion exhibits characteristic features such as a singlet ground state, enhanced double-bond character of the central C-N bonds, no reactivity toward water and methanol, and negative solvatochromic behavior.