Crystalline Radical Anion of a Diboratriazole and Its Conversion to a Neutral Radical Driven by a Carbene,Journal of the American Chemical Society

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Crystalline Radical Anion of a Diboratriazole and Its Conversion to a Neutral Radical Driven by a Carbene
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-07-21 , DOI: 10.1021/jacs.4c05777
Lizhao Zhu ₁ , Zhongtao Feng ₁ , Rei Kinjo ₁

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One-electron reduction of diboratriazole 1 with potassium graphite (KC₈) generates the radical anion 1^•–•K⁺, which undergoes a salt (KCl) elimination reaction upon addition of an N-heterocyclic carbene (NHC) to afford the neutral diboratriazole radical 3. An X-ray diffraction analysis, electron paramagnetic resonance spectroscopy, and computational studies revealed that an unpaired electron in radical species 1^•–•K⁺ and 3 is delocalized over the π-system of the B₂N₃ and carbene rings. Reversible oxidation of 3 gives rise to a diboratriazole cation 4 featuring a 6π aromatic character. Moreover, treating 1^•–•K⁺ with a half equivalent of a bis(NHC) produces a biradical species 5, in which there is little interaction between two radical moieties separated by the bis(NHC) linker, suggesting the dis-biradical property. 5 undergoes stepwise and reversible two-electron oxidation, establishing three formal oxidation states.

中文翻译：

二硼三唑的结晶自由基阴离子及其在卡宾驱动下转化为中性自由基

二硼三唑1用钾石墨 (KC ₈ ) 进行单电子还原，生成自由基阴离子1 ^•– • K ⁺ ，在添加N-杂环卡宾 (NHC) 后发生盐 (KCl) 消除反应，得到中性二硼三唑部首3 . X射线衍射分析、电子顺磁共振光谱和计算研究表明，自由基物种1 ^•– •K ⁺和3中的不成对电子在B ₂ N ₃和卡宾环的π系统上离域。 3的可逆氧化产生具有 6π 芳香特征的二硼三唑阳离子4 。此外，用半当量的双（NHC）处理1 ^•– •K ⁺会产生双自由基物质5 ，其中由双（NHC）连接体分隔的两个自由基部分之间几乎没有相互作用，表明双自由基特性。 5经历逐步且可逆的双电子氧化，建立三种形式的氧化态。

更新日期：2024-07-21

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