Mathew Jinu S, Klussmann Martin, Iwamura Hiroshi, Valera Fernando, Futran Alan, Emanuelsson Emma A C, Blackmond Donna G
Department of Chemistry, Imperial College, London SW7 2AZ, United Kingdom.
J Org Chem. 2006 Jun 23;71(13):4711-22. doi: 10.1021/jo052409i.
This Perspective highlights how the methodology of reaction progress kinetic analysis can provide a rapid and comprehensive kinetic profile of complex catalytic reaction networks under synthetically relevant conditions in a fraction of the number of experiments required by classical kinetic analysis. This approach relies on graphical manipulation of the extensive data sets available from accurate in situ monitoring of reaction progress under conditions where two concentration variables are changing simultaneously. A series of examples from Pd-catalyzed coupling reactions of aryl halides demonstrates how a wealth of kinetic information may be extracted from just three experiments in each case. Even before proposing a reaction mechanism, we can determine reaction orders in substrates, propose a resting state for the catalyst, and probe catalyst stability. Carrying out this kinetic analysis at the outset of a mechanistic investigation provides a framework for further work aimed at seeking a molecular-level understanding of the nature of the species within the catalytic cycle. To be considered plausible, any independent mechanistic proposal must be shown to be consistent with this global kinetic analysis.
这篇视角文章强调了反应进程动力学分析方法如何能够在合成相关条件下，以经典动力学分析所需实验数量的一小部分，快速且全面地给出复杂催化反应网络的动力学概况。该方法依赖于对在两个浓度变量同时变化的条件下通过准确原位监测反应进程所获得的大量数据集进行图形处理。一系列来自芳基卤化物钯催化偶联反应的例子表明，在每种情况下仅通过三个实验就可以提取出丰富的动力学信息。甚至在提出反应机理之前，我们就能确定底物的反应级数，提出催化剂的静止状态，并探究催化剂的稳定性。在机理研究开始时进行这种动力学分析，为进一步旨在从分子水平理解催化循环中物种性质的工作提供了一个框架。要被认为是合理的，任何独立的机理提议都必须与这种全局动力学分析一致。
