A Room-Temperature Stable Distonic Radical Cation
A Room-Temperature Stable Distonic Radical Cation
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室温稳定的二价自由基阳离子
DOI：
10.1002/anie.202011677
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发表时间：
2020-10-19
影响因子：
16.6
通讯作者：
Li, Zhongshu
中科院分区：
文献类型：
--
作者：
Chen, Xiaodan;Liu, Liu Leo;Li, Zhongshu
到目前为止，通过气相质谱仪和/或基质隔离光谱的工作，已经观察到具有空间分离的电荷和自由基位的远距离自由基阳离子(DRCs)。在这里，我们公开了一种结晶的二碳二磷酸盐的β-远端自由基阳离子Salt3(.+)(Barf)(barf=[B(3，5-(CF3)(2)C6H3)(4))](-))在室温下稳定，由单电子氧化诱导的分子内骨架重排反应形成。电子顺磁共振(EPR)谱、单晶X射线衍射谱、UV/Vis谱和密度泛函理论(DFT)计算证实了该物种的存在。化合物3(.+)(BarF)在两配位磷原子(0.74A.U)处显示出绝大多数的自旋密度。阳离子电荷主要位于由一个碳原子分隔的四配位磷原子(1.53A.U)上。这个物种代表了磷自由基阳离子的一个可分离的实体，它是迄今为止最接近真正的磷DRC的。
Distonic radical cations (DRCs) with spatially separated charge and radical sites have, so far, largely been observed by gas-phase mass spectrometry and/or matrix isolation spectroscopy work. Herein, we disclose the isolation of a crystalline dicarbondiphosphide-based beta-distonic radical cation salt3(.+)(BARF) (BARF=[B(3,5-(CF3)(2)C6H3)(4))](-)) stable at room temperature and formed by a one-electron-oxidation-induced intramolecular skeletal rearrangement reaction. Such a species has been validated by electron paramagnetic resonance (EPR) spectroscopy, single-crystal X-ray diffraction, UV/Vis spectroscopy and density functional theory (DFT) calculations. Compound3(.+)(BARF) exhibits a large majority of spin density at a two-coordinate phosphorus atom (0.74 a.u.) and a cationic charge located predominantly at the four-coordinate phosphorus atom (1.53 a.u.), which are separated by one carbon atom. This species represents an isolable entity of a phosphorus radical cation that is the closest to a genuine phosphorus DRC to date.