通过茚基-环戊二烯基自由基-自由基反应中的螺环芳基瞬态反应气相制备蒽 (C14H10) 的奇异反应动力学,Journal of the American Chemical Society

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通过茚基-环戊二烯基自由基-自由基反应中的螺环芳基瞬态反应气相制备蒽 (C14H10) 的奇异反应动力学
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-01-26 , DOI: 10.1021/jacs.2c12045
Chao He ₁ , Ralf I Kaiser ₁ , Wenchao Lu ₂ , Musahid Ahmed ₂ , Yahaira Reyes ₃ , Stanislaw F Wnuk ₃ , Alexander M Mebel ₃

Affiliation

_{1-茚基 (C 9} H ₇^• ) 自由基和环戊二烯基 (C ₅ H ₅^• ) 自由基之间的气相反应已首次使用基于同步加速器的质谱法与热解反应器相结合进行了研究。可调谐真空紫外光子的软光电离可用于菲、蒽和苯并富瓦烯 (C ₁₄ H _{10 ) 生产过程中的异构体选择性鉴定}). 文献中流行的经典理论提出自由基仅在其特定的自由基中心结合，我们发现了一种不寻常的反应途径，该途径涉及共振稳定的烃基与与传统碳原子相邻的芳基的无障碍结合C1激进中心；这种非常规加成之后通过一类奇异的螺环芳烃中间体大量异构化为菲和蒽。这一结果使人们对宇宙碳收支的演变有了更深入的了解，并为自下而上合成独特的螺环芳烃提供了新的方法，这可能与在深空合成更复杂的芳烃碳骨架有关。

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Exotic Reaction Dynamics in the Gas-Phase Preparation of Anthracene (C14H10) via Spiroaromatic Radical Transients in the Indenyl–Cyclopentadienyl Radical–Radical Reaction

The gas-phase reaction between the 1-indenyl (C₉H₇^•) radical and the cyclopentadienyl (C₅H₅^•) radical has been investigated for the first time using synchrotron-based mass spectrometry coupled with a pyrolytic reactor. Soft photoionization with tunable vacuum ultraviolet photons afforded for the isomer-selective identification of the production of phenanthrene, anthracene, and benzofulvalene (C₁₄H₁₀). The classical theory prevalent in the literature proposing that radicals combine only at their specific radical centers is challenged by our discovery of an unusual reaction pathway that involves a barrierless combination of a resonantly stabilized hydrocarbon radical with an aromatic radical at the carbon atom adjacent to the traditional C1 radical center; this unconventional addition is followed by substantial isomerization into phenanthrene and anthracene via a category of exotic spiroaromatic intermediates. This result leads to a deeper understanding of the evolution of the cosmic carbon budget and provides new methodologies for the bottom-up synthesis of unique spiroaromatics that may be relevant for the synthesis of more complex aromatic carbon skeletons in deep space.

更新日期：2023-01-26

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