Isolable Anion Radicals of Nitrosoarenes,Chinese Journal of Chemistry

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Isolable Anion Radicals of Nitrosoarenes
Chinese Journal of Chemistry ( IF 5.5 ) Pub Date : 2019-12-24 , DOI: 10.1002/cjoc.201900416
Dongyang Wang _{1,

2} , Masilamani Tamizmani ₁ , Xuebing Leng ₁ , Liang Deng _{1,

2}

Affiliation

The rich redox chemistry of nitrosoarenes has rendered these reactive molecules very useful in modern synthetic and material chemistry. Electrochemical studies have revealed the capability of nitrosoarenes to undergo one‐electron oxidation or reduction reaction for a long time. However, the isolation and structural characterization of nitrosoarene radical compounds deviating the stabilization of transition‐metal have not been achieved. Investigation on the reduction reaction of nitrosoarenes bearing steric demanding substituents has now revealed that the interaction of 2,6‐dimesityl‐1‐nitroso‐benzene (DmpNO) or 2,4,6‐tri(tert‐butyl)‐1‐nitroso‐benzene (TtpNO) with KC₈ and crypt‐2,2,2 can produce the corresponding anion radical compound [K(crypt‐2,2,2)][DmpNO] (1) or [K(crypt‐2,2,2)][TtpNO] (2) in good isolated yield. Compounds 1 and 2 represent the first examples of isolable nitrosoarene radical compounds deviating the stabilization of transition‐metal, and have been characterized by single‐crystal X‐ray diffraction study, electron paramagnetic resonance (EPR) spectroscopy, and elemental analysis. Theoretical study in collaboration with the characterization data revealed that the unpaired spin in [DmpNO]^•– and [TtpNO]^•– delocalizes on the nitroso and the central phenyl groups.

中文翻译：

亚硝基芳烃的可分离阴离子自由基

亚硝基芳烃的丰富的氧化还原化学反应使这些反应性分子在现代合成化学和材料化学中非常有用。电化学研究表明，亚硝基芳烃能够长时间进行单电子氧化或还原反应。但是，尚未实现亚硝基亚芳基自由基化合物的分离和结构表征，这些化合物破坏了过渡金属的稳定性。对带有空间要求取代基的亚硝基芳烃的还原反应的研究表明，2,6-二苯甲基-1-亚硝基苯（DmpNO）或2,4,6-三（叔丁基）-1-亚硝基的相互作用具有KC ₈和crypt-2,2,2的苯（TtpNO）可以产生相应的阴离子自由基化合物[K（crypt-2,2,2）] [DmpNO]（1）或[K（crypt-2,2,2）] [TtpNO]（2）的隔离率很高。化合物1和2代表了可分离的亚硝基芳烃自由基化合物的第一个实例，这些化合物偏离了过渡金属的稳定性，并已通过单晶X射线衍射研究，电子顺磁共振（EPR）光谱和元素分析进行了表征。与表征数据合作进行的理论研究表明，[DmpNO] ^•–和[TtpNO] ^•–中未成对的自旋在亚硝基和中心苯基上离域。

更新日期：2019-12-25

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