Protonated methylcyclopropane is an intermediate providing complete 13C-label scrambling at C4 olefin isomerization in zeolite
Protonated methylcyclopropane is an intermediate providing complete 13C-label scrambling at C4 olefin isomerization in zeolite
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DOI：
10.1016/j.checat.2022.100503
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发表时间：
2023-01
期刊：
影响因子：
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通讯作者：
Wei Chen;Mengdi Huang;Xianfeng Yi;Yu Hui;Pan Gao;Guangjin Hou;A. Stepanov;Yucai Qin;Lijuan Song;Shang-Bin Liu;Zhongfang Chen;Anmin Zheng
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文献类型：
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作者：
Wei Chen;Mengdi Huang;Xianfeng Yi;Yu Hui;Pan Gao;Guangjin Hou;A. Stepanov;Yucai Qin;Lijuan Song;Shang-Bin Liu;Zhongfang Chen;Anmin Zheng
Carbocations play crucial roles during catalytic reactions by dictating the reaction pathways and genuine mechanisms, but the instability of carbocations prevents thorough observations. The stabilization of carbocations would greatly help us gain a deep understanding of the reaction mechanisms. By means ofab initiomolecular dynamics (AIMD) simulations and anin situexperimental approach, a complete scrambling of13C-labeled C4=products was observed during the isomerization reaction in the H-ZSM-5 zeolite at room temperature, and the corner-protonated methylcyclopropanes (as a non-classical carbocation) featuring the three-center two-electron (3c–2e) bonds were confirmed to be the highly active metastable intermediates of C4isomerization. Our results not only uncover the nature of facile C shift in carbocations during zeolite-catalyzed reactions but also bring some fundamental understandings to carbocation chemistry in a zeolite confined environment.
