Laconsay Croix J, Mallick Dibyendu, Shaik Sason
Institute of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel.
Department of Chemistry, University of California-Davis, 1 Shields Avenue, Davis, California 95616, United States.
J Org Chem. 2021 Jan 1;86(1):731-738. doi: 10.1021/acs.joc.0c02322. Epub 2020 Dec 6.
The topic of this paper is whether the mechanism of the degenerate Cope rearrangement of semibullvalene can be affected by the presence of electrostatic fields. Herein, we report that the shape of the energy surface, as demonstrated by an "interrupted" (stepwise) mechanism, is altered in the presence of a copper cation, Cu. Natural bond-orbital and block-localized wave-function energy decomposition analyses suggest that orbital and electrostatic interactions play a major role in altering the shape of the energy surface. Applying additional external electric fields (EEFs) induces a significant change to the energy surface with Cu present but negligible effects in the absence of Cu. These findings are consistent with recent studies that demonstrate that EEFs more readily stabilize/destabilize systems with larger, more polarizable, dipole moments.
本文的主题是半富烯的简并科普重排机制是否会受到静电场的影响。在此，我们报告，如通过“中断”（逐步）机制所证明的，能量表面的形状在存在铜阳离子Cu的情况下会发生改变。自然键轨道和块定域波函数能量分解分析表明，轨道相互作用和静电相互作用在改变能量表面形状方面起主要作用。施加额外的外部电场（EEFs）会使存在Cu时的能量表面发生显著变化，但在不存在Cu时影响可忽略不计。这些发现与最近的研究一致，这些研究表明EEFs更容易使具有更大、更可极化偶极矩的系统稳定/不稳定。
