Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH₃ to CN under Extreme Conditions

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• 作者：Dr. Haiyan Zheng ; Dr. Kuo Li ; Dr. George D. Cody ; Dr. Christopher A. Tulk ; Dr. Xiao Dong ; Dr. Guoying Gao ; Jamie J. Molaison ; Dr. Zhenxian Liu ; Dr. Mikhail Feygenson ; Dr. Wenge Yang ; Dr. Ilia N. Ivanov ; Leonardo Basile ; Dr. Juan-Carlos Idrobo ; Dr. Malcolm Guthrie and Dr. Ho-kwang Mao
• 刊名：Angewandte Chemie International Edition
• 出版年：2016
• 出版时间：September 19, 2016
• 年：2016
• 卷：55
• 期：39
• 页码：12040-12044
• 全文大小：1341K
• ISSN：1521-3773

文摘

Acetonitrile (CH₃CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C−H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C−H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH₃ to CN along the CH⋅⋅⋅N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp² and sp³ bonded carbon. Finally, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C−H can be activated by high pressure, even at room temperature and without a catalyst.