在原子转移反应的速率上的固体效应的作用
Yi Sun1, Fengjiao Liu2, Jacob N Sanders3
1Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Rd, Cambridge CB21EW, England.
The Journal of organic chemistry
|August 21, 2023
概括
来自大型氧基的固体效应会影响原子转移 (HAT) 反应速率. 这些对激活障碍和反应度的固体效应是通过既定的关系很好地描述的,即使是与重的分子.
科学领域:
- 计算化学是一种计算化学.
- 化学动力学 化学动力学
背景情况:
- 原子转移 (HAT) 反应在许多化学过程中至关重要.
- 了解HAT反应中的固体效应对于预测反应结果很重要.
研究的目的:
- 通过计算来研究固体效应对氧基和基之间的HAT反应速率的影响.
- 确定大型替代剂如何影响激活障碍和反应度.
主要方法:
- 使用量子化学密度函数理论 (DFT) 来计算过渡状态.
- 分析激活障碍,反应和固体排斥效应.
主要成果:
- 巨大的基因替代剂显著影响激活障碍和反应度.
- 基上的替代物对这些反应参数的影响最小.
- 埃文斯 - 波兰尼关系仍然是HAT反应的良好描述,即使有硬质障碍.
- 在某些情况下,分散效应可以稳定过渡状态.
结论:
- 绝缘效应在涉及重氧基的HAT反应中起着重要作用.
- 已建立的动力模型,如埃文斯-波兰尼关系是强大的,适用于复杂的系统.
- 计算方法为硬质要求反应的机制和能量学提供了宝贵的见解.
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