Mechanistic Insights on Concentrated Lithium Salt/Nitroalkane Electrolyte Based on Analogy with Fluorinated Alcohols
Mechanistic Insights on Concentrated Lithium Salt/Nitroalkane Electrolyte Based on Analogy with Fluorinated Alcohols
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DOI：
10.1002/ejoc.201901576
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发表时间：
2020-02
影响因子：
2.8
通讯作者：
Naoki Shida;Y. Imada;Yohei Okada;K. Chiba
中科院分区：
文献类型：
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作者：
Naoki Shida;Y. Imada;Yohei Okada;K. Chiba
1，1，1，3，3，3-六氟-2-丙醇(HFIP)和2，2，2-三氟乙醇(TFE)等氟化醇已成为包括空穴催化在内的氧化化学中强有力的溶剂。本文介绍了锂盐/硝基烷烃电解液与氟化醇在电合成中的相似性。根据电合成、拉曼光谱、核磁共振光谱和循环伏安(CV)的结果，我们证明了锂离子、高氯酸盐或磺酰亚胺阴离子和硝基烷烃的结合是稳定自由基阳离子的理想溶液，就像氟化醇一样。循环伏安结果表明，1，4-二甲氧基苯的自由基阳离子在1.0mLiClO_4溶液中的稳定性比在HFIP溶液中的稳定性好。本文描述的这种电解液体系的机理建议将为设计适用于各种氧化化学的反应体系提供新的方向。
Fluorinated alcohols such as 1,1,1,3,3,3‐hexafluoro2‐propanol (HFIP) and 2,2,2‐trifluoroethanol (TFE) have emerged as powerful solvents in oxidation chemistry including hole catalysis. In this paper, we describe the similarity of lithium salt/nitroalkane electrolytes with fluorinated alcohols in electrosynthesis. Based on the results from electrosynthesis, Raman and nuclear magnetic resonance spectroscopy and cyclic voltammetry (CV), we have demonstrated that the combination of lithium cation, perchlorate or sulfonimide anions, and nitroalkanes make up an ideal solution to stabilize radical cations, just like fluorinated alcohols. The CV results suggested that the radical cation of 1,4‐dimethoxybenzene is better stabilized in 1.0mLiClO4than in a neat HFIP solution. A mechanistic proposal for this electrolyte system described herein will give new directions for designing reaction systems for a wide range of oxidation chemistries.