Can Strained Hydrocarbons Be “Forced” To Be Stable?,The Journal of Physical Chemistry A

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Can Strained Hydrocarbons Be “Forced” To Be Stable?
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2016-08-31 00:00:00 , DOI: 10.1021/acs.jpca.6b05461
Tim Stauch ₁ , Benjamin Günther ₂ , Andreas Dreuw ₁

Affiliation

Many strained hydrocarbons are prone to isomerization, dimerization, and trimerization under normal laboratory conditions. Here we investigate a method to stabilize angle-strained cycloalkynes by applying a mechanical pulling force to the carbon atoms adjacent to the triple bond, which partially linearizes the C≡C–C bond angles. We discuss various methods of applying such pulling forces, including photoswitches and incorporation into additional strained macrocycles. We use the computational JEDI (Judgement of Energy DIstribution) analysis to quantify the distribution of energy in strained cycloheptyne and judge the change in stability upon application of an external force via isodesmic and homodesmotic reactions. We find that cycloheptyne can indeed be stabilized by external forces. However, the force generated by photoswitches during isomerization is too low to lead to a significant stabilization of the molecule. Hence, stronger forces are needed, which can be achieved by incorporating cycloheptyne into a second strained macrocycle.

中文翻译：

张力碳氢化合物能否被“强制”稳定？

在正常实验室条件下，许多应变烃均易于异构化，二聚化和三聚化。在这里，我们研究了通过对与三键相邻的碳原子施加机械拉力来稳定角应变环炔烃的方法，该方法部分线性化了C≡C–C键角。我们讨论了施加这种拉力的各种方法，包括光开关以及将其并入其他应变大环中。我们使用计算的JEDI（能量分布的判断）分析来量化应变环庚炔中的能量分布，并通过等渗和同渗反应通过施加外力来判断稳定性的变化。我们发现，环庚炔确实可以通过外力稳定。然而，光开关在异构化过程中产生的力太低，无法导致分子的显着稳定。因此，需要更强的力，这可以通过将环庚炔并入第二应变大环中来实现。

更新日期：2016-08-31

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