Benzene Radical Anion in the Context of the Birch Reduction: When Solvation Is the Key.,The Journal of Physical Chemistry Letters

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Benzene Radical Anion in the Context of the Birch Reduction: When Solvation Is the Key.
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2020-07-06 , DOI: 10.1021/acs.jpclett.0c01505
Krystof Brezina _{1,

2} , Pavel Jungwirth ₂ , Ondrej Marsalek ₁

Affiliation

The benzene radical anion is an important intermediate in the Birch reduction of benzene by solvated electrons in liquid ammonia. Beyond organic chemistry, it is an intriguing subject of spectroscopic and theoretical studies due to its rich structural and dynamical behavior. In the gas phase, the species appears as a metastable shape resonance, while in the condensed phase, it remains stable. Here, we approach the system by ab initio molecular dynamics in liquid ammonia and demonstrate that the inclusion of solvent is crucial and indeed leads to stability. Beyond the mere existence of the radical anion species, our simulations explore its condensed-phase behavior at the molecular level and offer new insights into its properties. These include the dynamic Jahn–Teller distortions, vibrational spectra in liquid ammonia, and the structure of the solvent shell, including the motif of a π-hydrogen bond between ammonia molecules and the aromatic ring.

中文翻译：

桦木还原中的苯自由基阴离子：溶剂化是关键。

苯自由基阴离子是在液态氨中通过溶剂化电子将苯桦木还原的重要中间体。除了有机化学之外，由于其丰富的结构和动力学行为，它也是光谱学和理论研究的一个有趣的主题。在气相中，物质表现为亚稳态形状共振，而在冷凝相中，物质保持稳定。在这里，我们从头开始处理系统液氨中的分子动力学，证明了溶剂的加入是至关重要的，并确实导致了稳定性。除了自由基阴离子种类的存在以外，我们的模拟还探索了其在分子水平上的凝聚相行为，并为其性质提供了新的见解。这些包括动态的Jahn–Teller畸变，液氨中的振动光谱以及溶剂壳的结构，包括氨分子与芳环之间的π-氢键基序。

更新日期：2020-08-06

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