Kinetics of primary mechanochemical covalent-bond-forming reactions

Yerzhan S. Zholdassov, Ryan W. Kwok, Milan A. Shlain, Monil Patel, Mateusz Marianski and Adam B. Braunschweig
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Abstract

Mechanical activation of reactions can reduce significantly the amounts of solvent and energy required to form covalent organic bonds. Despite growing interest in the field of mechanochemistry and increasing reports of mechanochemical synthesis of organic molecules, the fundamental question of how stresses activate covalent-bond-forming (CBF) reactions remains unresolved. This question remains unresolved because of the difficulties involved in measuring the applied forces and the reaction times in mechanochemical reactors, and the challenges related to deconvoluting microscopic (primary) and macroscopic (secondary) processes in the analysis of reaction kinetics. Here we discuss the use nanoscopic probe-microscope tips to explore the kinetics of CBF reactions. Because these experiments examine reactions on monolayers, surfaces, or nanoscopic particles, they circumvent secondary processes to isolate how stress affects the rates of the primary, CBF events. The major result of these studies is an emerging consensus that stress accelerates reactions by distorting organic molecules and in doing so, lowers reaction activation energies and alters reaction trajectories. This new understanding of how stresses activate reactions can be used to predict the outcomes of CBF mechanochemical reactions, which will lead to the wider adoption of sustainable mechanochemical processes by the synthetic community.

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初级机械化学共价键形成反应动力学
机械激活反应可以大大减少形成共价有机键所需的溶剂和能量。尽管人们对机械化学领域的兴趣与日俱增,有关有机分子机械化学合成的报道也越来越多,但应力如何激活共价键形成(CBF)反应这一基本问题仍未得到解决。这个问题之所以悬而未决,是因为测量机械化学反应器中的作用力和反应时间非常困难,而且在分析反应动力学时,还面临着将微观(一级)过程和宏观(二级)过程进行分解的挑战。在此,我们讨论使用纳米探针-显微镜尖端探索 CBF 反应动力学。由于这些实验研究的是单层、表面或纳米颗粒上的反应,因此它们避开了次要过程,从而分离出应力如何影响主要的 CBF 事件的速率。这些研究的主要成果是形成了一种共识,即应力通过扭曲有机分子加速反应,从而降低反应活化能并改变反应轨迹。这种对应力如何激活反应的新认识可用于预测 CBF 机械化学反应的结果,这将促使合成界更广泛地采用可持续的机械化学工艺。
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