对C=C,C=O和C=S双键的甲基添加的动力学和热力学进行比较
David J Henry1, Michelle L Coote, Rodolfo Gómez-Balderas
1Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia. djhenry@rsc.anu.edu.au
Journal of the American Chemical Society
|February 12, 2004
概括
研究了对基,碳基和硫基的基添加. 反应障碍是了解速率的关键,添加通常有利于碳中心.
科学领域:
- 计算化学的计算化学
- 化学动力学 化学动力学
- 反应机制 反应机制
背景情况:
- 了解激素添加反应对于化学合成和大气化学至关重要.
- 之前的研究已经探索了激进的添加,但需要对不同不和系统进行全面的分析.
研究的目的:
- 研究甲基基向基,碳基和硫基添加的障碍物,度和速率常数.
- 为了分析反向β分裂反应.
- 用曲线交叉模型合理化发现.
主要方法:
- 使用高水平的初始计算来确定反应的能量和动力学.
- 曲线交叉模型被用来合理化观察到的趋势.
- 分析包括添加和β分裂反应的障碍物,和速率常数.
主要成果:
- 添加反应通过早期的过渡结构进行.
- 对于C=C键,添加障碍主要是由外热性驱动的,有利于非替代碳.
- 对于C=O键,障碍取决于外热度和单点三点差距,有利于碳添加.
- 对于硫基,碳添加在热力学上是有利的,但由于旋转密度,硫添加具有较低的动力障碍.
结论:
- 反应速率主要由激活障碍决定,因为差异很小.
- 在这些系统中,增加碳中心通常在动力学和热力学上是最受欢迎的.
- 旋转密度在确定 thiocarbonyls 的反应途径方面发挥着重要作用.
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