Porphyrin‐Stabilized Nitrenium Dication,Chemistry - A European Journal

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Porphyrin‐Stabilized Nitrenium Dication
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2018-12-13 , DOI: 10.1002/chem.201805491
Keisuke Fujimoto ₁ , Daiki Shimizu ₁ , Atsuhiro Osuka ₁

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An azepine‐fused Ni^II‐porphyrin dimer was synthesized by oxidative amination of β–β linked Ni^II‐porphyrin dimer, and its N‐aryl congener was synthesized by twofold Buchwald–Hartwig amination of β‐to‐β linked and dichlorinated Ni^II‐porphyrin dimer. Oxidation of the NH congener gave neutral aminyl radical and nitrenium ion successively in a similar manner to the previously reported NH‐bridged Ni^II‐porphyrin dimer. Oxidation of the N‐aryl congener afforded formal nitrenium dication in a single‐step two‐electron oxidation. Stable nitrenium dications that are isoelectronic to neutral trivalent boron compounds and tertiary carbocations are rare. The chemical stability of the nitrenium dication was improved by chlorine substitution at the most reactive β‐position. The structural, optical, magnetic, electrochemical properties of these compounds were fully characterized.

中文翻译：

卟啉稳定的硝化阳离子

一个氮杂-稠合镍^II -卟啉二聚体是通过β-β的氧化胺化合成联的Ni ^II -卟啉二聚体，以及其Ñ -芳基同系物是由β-到-β联双重Buchwald-Hartwig偶联反应合成，二氯化镍^II卟啉二聚体。NH同源物的氧化以与先前报道的NH桥键的Ni ^II-卟啉二聚体相似的方式连续产生中性的氨基自由基和亚硝酸根离子。氮的氧化芳基同类物通过一步两电子氧化提供了正式的亚硝基指示。等电于中性三价硼化合物和叔碳正离子的稳定的氮离子很少见。通过在最具反应性的β位置进行氯取代，改善了硝鎓盐的化学稳定性。这些化合物的结构，光学，磁性，电化学性质已得到充分表征。

更新日期：2018-12-13

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