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Cyclic (Amino)(Aryl)Nitrenium Cations with Lewis Acidity Controlled by Remote Substituents

Cyclic (Amino)(Aryl)Nitrenium Cations with Lewis Acidity Controlled by Remote Substituents N‐Heterocyclic nitrogen Lewis acids are important in synthetic chemistry. Stable cyclic (amino)(aryl)nitrenium cations, cyc‐1+—cyc‐3+, were synthesized by chemical oxidation of aryl azo compounds with different substituents, iPr, H and I, at the para positions of the phenyl group. The excited triplet states of cyc‐1+—cyc‐3+ abstract H‐atoms step by step to generate radical intermediates cyc‐1H•+—cyc‐3H•+ traced by EPR spectroscopy and products cyc‐1H2+—cyc‐3H2+ characterized by single crystal X‐ray diffraction. The Lewis acidity of species cyc‐1+—cyc‐3+ are remote substituent‐dependent. Cyc‐2+—cyc‐3+ have much higher acidity than those previously reported congeners based on energies of LUMOs. The electrophilicity enables them to form Lewis adducts with neutral Lewis base Me3P, and to gain one‐electron to produce neutral radicals cyc‐1•—cyc‐3•. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Chinese Journal of Chemistry Wiley

Cyclic (Amino)(Aryl)Nitrenium Cations with Lewis Acidity Controlled by Remote Substituents

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References (16)

Publisher
Wiley
Copyright
© 2022 SIOC, CAS, Shanghai, & WILEY‐VCH GmbH
ISSN
1001-604X
eISSN
1614-7065
DOI
10.1002/cjoc.202100690
Publisher site
See Article on Publisher Site

Abstract

N‐Heterocyclic nitrogen Lewis acids are important in synthetic chemistry. Stable cyclic (amino)(aryl)nitrenium cations, cyc‐1+—cyc‐3+, were synthesized by chemical oxidation of aryl azo compounds with different substituents, iPr, H and I, at the para positions of the phenyl group. The excited triplet states of cyc‐1+—cyc‐3+ abstract H‐atoms step by step to generate radical intermediates cyc‐1H•+—cyc‐3H•+ traced by EPR spectroscopy and products cyc‐1H2+—cyc‐3H2+ characterized by single crystal X‐ray diffraction. The Lewis acidity of species cyc‐1+—cyc‐3+ are remote substituent‐dependent. Cyc‐2+—cyc‐3+ have much higher acidity than those previously reported congeners based on energies of LUMOs. The electrophilicity enables them to form Lewis adducts with neutral Lewis base Me3P, and to gain one‐electron to produce neutral radicals cyc‐1•—cyc‐3•.

Journal

Chinese Journal of ChemistryWiley

Published: Feb 1, 2022

Keywords: Nitrenium cation; Acidity; Radicals; Excited triplet state; Electrophilicity

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