radical anion
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2022 ◽  
Author(s):  
Shusaku Ukai ◽  
Norihito Fukui ◽  
Takahisa Ikeue ◽  
Hiroshi Shinokubo

2022 ◽  
Vol 13 (1) ◽  
Author(s):  
Yujing Guo ◽  
Chao Pei ◽  
Rene M. Koenigs

AbstractNitrene transfer reactions represent one of the key reactions to rapidly construct new carbon-nitrogen bonds and typically require transition metal catalysts to control the reactivity of the pivotal nitrene intermediate. Herein, we report on the application of iminoiodinanes in amination reactions under visible light photochemical conditions. While a triplet nitrene can be accessed under catalyst-free conditions, the use of a suitable photosensitizer allows the access of a nitrene radical anion. Computational and mechanistic studies rationalize the access and reactivity of triplet nitrene and nitrene radical anion and allow the direct comparison of both amination reagents. We conclude with applications of both reagents in organic synthesis and showcase their reactivity in the reaction with olefins, which underline their markedly distinct reactivity. Both reagents can be accessed under mild reaction conditions at room temperature without the necessity to exclude moisture or air, which renders these metal-free, photochemical amination reactions highly practical.


Author(s):  
Jenifer S. Calvo ◽  
Rhiza Lyne E. Villones ◽  
Nicholas J. York ◽  
Ewelina Stefaniak ◽  
Grace E. Hamilton ◽  
...  
Keyword(s):  

2022 ◽  
Vol 92 (2) ◽  
pp. 258
Author(s):  
А.И. Александров ◽  
В.Г. Шевченко ◽  
С.С. Абрамчук ◽  
С.Б. Зезин ◽  
С.В. Фокин ◽  
...  

Composites of heterospin molecular magnet [EuIII(SQ)3bipy] in a polystyrene (PS) matrix have been synthesized. This complex [EuIII(SQ)3bipy] contains four paramagnetic centers - the Eu3+ ion and three SQ ligands (SQ—3,6-di-tert-butyl benzoquinone radical anion); bipy (bipyridyl) is diamagnetic. It has been established that intensive mechanical activation of [EuIII(SQ)3bipy]/PS samples leads to an reological explosion, as a result of which radio frequency superradiance, the appearance of free electrons and the formation of Eu metal nanoparticles are observed. The duration of this process is 10 ns.


2022 ◽  
Author(s):  
Nikita R. Romanenko ◽  
Alexey V. Kuzmin ◽  
Salavat S. Khasanov ◽  
Maxim A. Faraonov ◽  
Evgeniya I. Yudanova ◽  
...  

Coordination of tin(II) phthalocyanine to transition metal carbonyl clusters in neutral {Sn(II){Pc(2-)}}(0) or radical anion {Sn(II){Pc(•3-)}}(-) states is reported. Direct interaction of Co4(CO)12 with {Sn(II){Pc(2-)}}(0) yields crystalline complex {Co4(CO)11·Sn(II){Pc(2-))} (1)....


Author(s):  
Krisztina Kovács ◽  
Tünde Tóth ◽  
László Wojnárovits

Abstract This study summarizes the results of scientific investigations on the removal of the three most-often used ß-blockers (atenolol, metoprolol and propranolol) by various advanced oxidation processes (AOP). The free radical chemistry, rate constants, degradation mechanism and elimination effectiveness of these compounds are discussed together with the technical details of experiments. In most of AOP the degradation is predominantly initiated by hydroxyl radicals. In sulfate radical anion based oxidation processes (SROP) both hydroxyl radical and sulfate radical anion greatly contributes to the degradation. The rate constants of reactions with these two radicals are in the 109–1010 M−1 s−1 range. The degradation products reflect ipso attack, hydroxylation on the aromatic ring and/or the amino moiety and cleavage of the side chain. Among AOP photocatalysis and SROP are the most effective for degradation of the three ß-blockers. The operating parameters have to be optimized to the most suitable effectiveness.


Author(s):  
Krystof Brezina ◽  
Vojtech Kostal ◽  
Pavel Jungwirth ◽  
Ondrej Marsalek

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Dong Zou ◽  
Lishe Gan ◽  
Fan Yang ◽  
Huan Wang ◽  
Youge Pu ◽  
...  

AbstractThe use of nitroarenes as amino sources in synthesis is challenging. Herein is reported an unusual, straightforward, and transition metal-free method for the net [3 + 2]-cycloaddition reaction of 2-azaallyl anions with nitroarenes. The products of this reaction are diverse 2,5-dihydro-1,2,4-oxadiazoles (>40 examples, up to 95% yield). This method does not require an external reductant to reduce nitroarenes, nor does it employ nitrosoarenes, which are often used in N–O cycloadditions. Instead, it is proposed that the 2-azaallyl anions, which behave as super electron donors (SEDs), deliver an electron to the nitroarene to generate a nitroarene radical anion. A downstream 2-azaallyl radical coupling with a newly formed nitrosoarene is followed by ring closure to afford the observed products. This proposed reaction pathway is supported by computational studies and experimental evidence. Overall, this method uses readily available materials, is green, and exhibits a broad scope.


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