化的相关热力学和动力学水性
Matthew R Espinosa1, Mehmed Z Ertem2, Mariam Barakat3
1Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520, United States.
Journal of the American Chemical Society
|September 21, 2022
概括
该研究研究了从复合体到各种受体的化物转移反应. 虽然热力学驱动力通常会增加反应速度,但固态因素会显著影响化物转移动力学,这对催化剂设计至关重要.
科学领域:
- 有机金属化学 有机金属化学
- 反应动力学反应动力学
- 计算化学计算化学
背景情况:
- 了解化物转移是催化剂的关键.
- 二 Pyridine 复合体是相关的化物供体.
- 预测反应速率需要了解热力学和动力学因素.
研究的目的:
- 确定从Re(R-bpy) ((CO) 3H复合物中转移化物的动力学.
- 为了确定这些复合物的热力学水性.
- 为了关联动力学和热力学参数,并探索影响化物转移速率的因素.
主要方法:
- 对化物转移到CO2和N异环的动力学研究.
- 计算方法 (DFT) 来确定热力学水度.
- 使用线性自由能量关系 (LFER),动态同位素效应,哈梅特分析和Bronsted α值进行分析.
主要成果:
- 化物转移率通常随着热力学驱动力的增加而增加.
- 动态同位素效应因驱动力而异,从反向到正常.
- 哈梅特分析显示,随着驱动力的增加,对电子效应的敏感性降低.
- 布朗斯特德α值和DFT建议协调,马库斯理论适用的反应.
- 立体效应显著偏离预测速度,突出了热力学预测的局限性.
结论:
- 热力学驱动力是化物转移速率的重要,但不是唯一的预测因素.
- 固态因子在调节反应动力学方面发挥着至关重要的作用.
- 催化剂设计必须考虑热力学和硬化影响,以获得最佳性能.
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