Intramolecular proton transfer in the isomerization of hydroxyacetone: Characterization based on reaction force analysis and the bond fragility spectrum
Intramolecular proton transfer in the isomerization of hydroxyacetone: Characterization based on reaction force analysis and the bond fragility spectrum
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DOI：
10.1002/qua.26269
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发表时间：
2020-09
影响因子：
2.2
通讯作者：
Huiet Joseph;Wallace D. Derricotte
中科院分区：
文献类型：
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作者：
Huiet Joseph;Wallace D. Derricotte
在M06‐2X/6‐311++G（d,p）理论水平的反作用力分析框架下，研究了羟丙酮异构化成2‐羟丙醇的机理。本文考虑了三种独特的途径：(a)通过它们共享的烯二醇中间体的Z -异构体形成的步进机制，(b)烯二醇E -异构体形成的步进机制，以及(c)绕过烯二醇中间体的协同途径。能量计算表明，协同路径的活化能势垒最低，为45.7 kcal mol−1。计算每个反应的反作用力、化学势和反应电子通量，以表征整个反应机制的电子变化。为了研究分子内质子转移的同步/异步性质，计算了反作用力常数。通过计算每个机制的键脆性谱，提供了同步性的附加表征。
The mechanism of isomerization of hydroxyacetone to 2‐hydroxypropanal is studied within the framework of reaction force analysis at the M06‐2X/6‐311++G(d,p) level of theory. Three unique pathways are considered: (a) a step‐wise mechanism that proceeds through the formation of the Z‐isomer of their shared enediol intermediate, (b) a step‐wise mechanism that forms the E‐isomer of the enediol, and (c) a concerted pathway that bypasses the enediol intermediate. Energy calculations show that the concerted pathway has the lowest activation energy barrier at 45.7 kcal mol−1. The reaction force, chemical potential, and reaction electronic flux are calculated for each reaction to characterize electronic changes throughout the mechanism. The reaction force constant is calculated in order to investigate the synchronous/asynchronous nature of the concerted intramolecular proton transfers involved. Additional characterization of synchronicity is provided by calculating the bond fragility spectrum for each mechanism.