Sun Cuihong, Xu Baoen, Zeng Yanli
Shijiazhuang Key Laboratory of Low Carbon Energy Materials, Technology Innovation Center of HeBei for Heterocyclic Compound, College of Chemical Engineering, Shijiazhuang University, Shijiazhuang 050035, P. R. China.
College of Chemistry and Materials Science, Hebei Normal University, Shijiazhuang 050024, P.R. China.
Phys Chem Chem Phys. 2024 Mar 20;26(12):9524-9533. doi: 10.1039/d3cp06115a.
Criegee intermediates (CIs), the key intermediates in the ozonolysis of olefins in atmosphere, have received much attention due to their high activity. The reaction mechanism of the most simple Criegee intermediate CHOO with vinyl alcohol (VA) was investigated by using the HL//M06-2X/def2TZVP method. The temperature and pressure dependent rate constant and product branching ratio were calculated using the master equation method. For CHOO + -VA, 1,4-insertion is the main reaction channel while for the CHOO + -VA, cycloaddition and 1,2-insertion into the O-H bond are more favorable than the 1,4-insertion reaction. The 1,4-insertion or cycloaddition intermediates are stabilized collisionally at 300 K and 760 torr, and the dissociation products involving OH are formed at higher temperature and lower pressure. The rate constants of the CHOO reaction with -VA and -VA both show negative temperature effects, and they are 2.95 × 10 and 2.07 × 10 cm molecule s at 300 K, respectively, and the former is agreement with the prediction in the literature.
克里吉中间体（CIs）是大气中烯烃臭氧分解的关键中间体，因其高活性而备受关注。采用HL//M06 - 2X/def2TZVP方法研究了最简单的克里吉中间体CHOO与乙烯醇（VA）的反应机理。使用主方程法计算了温度和压力依赖的速率常数及产物分支比。对于CHOO + -VA，1,4 -插入是主要反应通道，而对于CHOO + -VA，环加成和1,2 -插入到O - H键比1,4 -插入反应更有利。1,4 -插入或环加成中间体在300 K和760托下通过碰撞得以稳定，涉及OH的解离产物在较高温度和较低压力下形成。CHOO与 -VA和 -VA反应的速率常数均呈现负温度效应，在300 K时分别为2.95×10和2.07×10 cm³分子⁻¹ s⁻¹，前者与文献中的预测相符。
