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Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH 3 to CN under Extreme Conditions
Author(s) -
Zheng Haiyan,
Li Kuo,
Cody George D.,
Tulk Christopher A.,
Dong Xiao,
Gao Guoying,
Molaison Jamie J.,
Liu Zhenxian,
Feygenson Mikhail,
Yang Wenge,
Ivanov Ilia N.,
Basile Leonardo,
Idrobo JuanCarlos,
Guthrie Malcolm,
Mao Hokwang
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201606198
Subject(s) - chemistry , acetonitrile , catalysis , polymerization , polymer chemistry , dimer , triple bond , hydrogen bond , hydrogen , photochemistry , polymer , molecule , organic chemistry , double bond
Acetonitrile (CH 3 CN) 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 CH 3 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 sp 2 and sp 3 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.