Influence of stepwise oxidation on the structure, stability, and properties of planar pentacoordinate carbon species CAl5.,Physical Chemistry Chemical Physics

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Influence of stepwise oxidation on the structure, stability, and properties of planar pentacoordinate carbon species CAl5.
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2020-06-08 , DOI: 10.1039/d0cp01106a
Rui Sun ₁ , Xue-Feng Zhao , Bo Jin , Bin Huo , Jian-Hong Bian , Xiao-Ling Guan , Caixia Yuan , Yan-Bo Wu

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Computational design has played an important role in planar hyper-coordinate carbon (phC) chemistry. However, none of numerous computationally predicted phC species were subsequently successfully synthesized in the condensed phase, perhaps due to the frustrating issue of oxidation. In the present work, we studied the influence of stepwise oxidation on the structure, stability, and properties of phC species using the milestone planar pentacoordinate carbon (ppC) species CAl₅⁺ as an example. Our results indicated that the ppC structure of CAl₅⁺ would be directly destroyed with one, two, or six O atom(s) per molecule present and indirectly with three or four O atoms, but maintained with five O atoms due to the ppC isomer of CAl₅O₅⁺ being a kinetically stable global energy minimum displaying σ and π double aromaticity. Moreover, the magnitudes of the first to fifth vertical oxygen affinities (VOAs) for CAl₅⁺ were determined to be very high (−85.5 to −116.3 kcal mol⁻¹), probably due to the existence of peripheral diffuse Al–Al bond(s). However, the sixth VOA was reduced significantly to −50.2 kcal mol⁻¹, consistent with the absence of any diffuse Al–Al bond in the corresponding CAl₅O₅⁺ species. So CAl₅O₅⁺ may be insensitive to oxidation. Therefore, the ppC species D_5h CAl₅O₅⁺ might be resistant to being degraded under a delicate control of oxidation level (producing five O atoms per CAl₅⁺ molecule).

中文翻译：

逐步氧化对平面五配位碳原子CAl5的结构，稳定性和性能的影响。

计算设计在平面超坐标碳（phC）化学中发挥了重要作用。然而，可能是由于令人沮丧的氧化问题，因此在冷凝相中没有成功地计算出许多计算预测的phC物种。在本工作中，我们以具有里程碑意义的平面五配位碳（ppC）物种CAl ₅⁺为例研究了逐步氧化对phC物种的结构，稳定性和性能的影响。我们的结果表明，每个分子中存在的一个分子，一个，两个或六个O原子可直接破坏CAl ₅⁺的ppC结构，而由三个或四个O原子间接破坏CAl ₅⁺的ppC结构，但由于ppC异构体而被五个O原子维持铝₅ O₅⁺是显示出σ和π双重芳香度的动力学稳定的全局最小能量。此外，确定CAl₅⁺的第一至第五垂直氧亲和力（VOA）的量级非常高（-85.5至-116.3 kcal mol^-1），这可能是由于存在周边扩散的Al-Al键（ s）。但是，第六次VOA显着降低至-50.2 kcal mol^-1，这与相应的CAl₅ O₅⁺物种中没有任何弥散的Al-Al键相一致。因此，CAl₅ O₅⁺可能对氧化不敏感。因此，ppC种类D _5h CAl₅ O₅⁺可能难以在氧化水平的精细控制下降解（每个CAl₅⁺分子产生5个O原子）。

更新日期：2020-08-05

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