School of Science, Key Laboratory of High Performance Scientific Computation, Xihua University, Chengdu, 610039, P. R. China.
College of Pharmacy, Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of Ministry of Education, Hebei University, Baoding, 071002, P. R. China.
J Phys Chem Lett. 2021 Jul 22;12(28):6486-6491. doi: 10.1021/acs.jpclett.1c01619. Epub 2021 Jul 9.
In 2019, Diaz-Urrutia and Ott developed a high-yield method for direct conversion of methane to methanesulfonic acid and proposed a cationic chain reaction mechanism. However, Roytman and Singleton questioned this mechanism, and they favored a free-radical mechanism. In the present paper, we studied both the cationic chain and radical mechanisms and found the radical mechanism is more favorable, since it has a much lower energy barrier. However, the radical mechanism has not considered the effect of ions for the reaction taking place in oleum. Thus, we studied a simple model of a protonated radical mechanism, which further lowers the energy barrier. Although the true mechanism for the CH + SO reaction could be more complicated in electrolyte solutions, this model should be helpful for the further study of the mechanism of this reaction.
2019 年，迪亚兹-乌鲁蒂亚（Diaz-Urrutia）和奥特（Ott）开发了一种将甲烷直接转化为甲磺酸的高产率方法，并提出了阳离子链式反应机制。然而，罗伊特曼（Roytman）和辛格尔顿（Singleton）对该机制提出质疑，他们赞成自由基机制。在本文中，我们研究了阳离子链和自由基机制，发现自由基机制更有利，因为它的能垒低得多。然而，自由基机制没有考虑到在发烟硫酸中发生反应的离子的影响。因此，我们研究了一个质子化自由基机制的简单模型，该模型进一步降低了能垒。尽管在电解质溶液中，CH+SO 反应的真实机制可能更为复杂，但该模型应该有助于进一步研究该反应的机制。
