Department of Chemistry, The Scripps Research Institute , La Jolla, California 92037 United States.
J Am Chem Soc. 2015 Sep 2;137(34):10852-66. doi: 10.1021/jacs.5b05841. Epub 2015 Aug 18.
The use of modern kinetic tools to obtain virtually continuous reaction progress data over the course of a catalytic reaction opens up a vista that provides mechanistic insights into both simple and complex catalytic networks. Reaction profiles offer a rate/concentration scan that tells the story of a batch reaction time course in a qualitative "fingerprinting" manner as well as in quantitative detail. Reaction progress experiments may be mathematically designed to elucidate catalytic rate laws from only a fraction of the number of experiments required in classical kinetic measurements. The information gained from kinetic profiles provides clues to direct further mechanistic analysis by other approaches. Examples from a variety of catalytic reactions spanning two decades of the author's work help to delineate nuances on a central mechanistic theme.
现代动力学工具的使用可以在催化反应过程中获得几乎连续的反应进度数据,这为深入了解简单和复杂的催化网络提供了新的视角。反应谱提供了一个速率/浓度扫描,以定性的“指纹”方式以及定量细节描述了分批反应时间历程的故事。反应进度实验可以通过数学设计,从经典动力学测量所需实验数量的一小部分中阐明催化速率定律。从动力学谱中获得的信息为通过其他方法进行进一步的机理分析提供了线索。作者 20 年来在各种催化反应中的实例有助于阐明一个核心机理主题的细微差别。