A Room Temperature Stable Distonic Radical Cation.,Angewandte Chemie International Edition

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A Room Temperature Stable Distonic Radical Cation.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-09-10 , DOI: 10.1002/anie.202011677
Xiaodan Chen ₁ , Liu Leo Liu ₂ , Shihua Liu _{3,

4} , Hansjörg Grützmacher _{3,

4,

5} , Zhongshu Li _{3,

4}

Affiliation

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 β‐distonic radical cation salt 3^.+(BARF) (BARF=[B(3,5‐(CF₃)₂C₆H₃)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. Compound 3^.+(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.

中文翻译：

室温稳定的爆裂性自由基阳离子。

到目前为止，通过气相质谱法和/或基质分离光谱法可以观察到具有空间上分离的电荷和自由基位点的tonic自由基阳离子（DRC）。在这里，我们公开了基于结晶二碳二磷的β-二歧自由基阳离子盐3 ^。+（BARF）（BARF = [B（3,5-（CF ₃）₂ C ₆ H ₃）₄）] ^-的分离）在室温下稳定并由单电子氧化诱导的分子内骨骼重排反应形成。此类物质已通过电子顺磁共振（EPR）光谱，单晶X射线衍射，UV / Vis光谱和密度泛函理论（DFT）计算得到了验证。化合物3 ^。+（BARF）在两个配位的磷原子（0.74 au）处表现出很大的自旋密度，并且主要位于四个配位的磷原子处（1.53 au）处的阳离子电荷，它们之间被一个碳原子隔开。该物质表示迄今为止最接近真正的磷DRC的磷自由基阳离子的可分离实体。

更新日期：2020-09-10

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