title: Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions.
abstract: Acetonitrile (CH3 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 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 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.
authors: Center for High Pressure Science and Technology Advanced Research, Beijing, 100094, P.R. China.
authors: Haiyan
authors: H
authors: Zheng
authors: Center for High Pressure Science and Technology Advanced Research, Beijing, 100094, P.R. China. likuo@hpstar.ac.cn.|Geophysical Laboratory, Carnegie Institution of Washington, Washington, DC, 20015, USA. likuo@hpstar.ac.cn.
authors: Kuo
authors: K
authors: Li
authors: Geophysical Laboratory, Carnegie Institution of Washington, Washington, DC, 20015, USA.
authors: George D
authors: GD
authors: Cody
authors: Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA.
authors: Christopher A
authors: CA
authors: Tulk
authors: Center for High Pressure Science and Technology Advanced Research, Beijing, 100094, P.R. China.
authors: Xiao
authors: X
authors: Dong
authors: Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, 14853, USA.|State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, TX, 066004, P.R. China.
authors: Guoying
authors: G
authors: Gao
authors: Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA.
authors: Jamie J
authors: JJ
authors: Molaison
authors: Geophysical Laboratory, Carnegie Institution of Washington, Washington, DC, 20015, USA.
authors: Zhenxian
authors: Z
authors: Liu
authors: Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA.|Jülich Center for Neutron Science, Forschungszentrum Jülich GmbH, D-52425, Jülich, Germany.
authors: Mikhail
authors: M
authors: Feygenson
authors: Center for High Pressure Science and Technology Advanced Research, Beijing, 100094, P.R. China.|HPSynC, Geophysical Laboratory, Carnegie Institution of Washington, Argonne, IL, 60439, USA.
authors: Wenge
authors: W
authors: Yang
authors: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA.
authors: Ilia N
authors: IN
authors: Ivanov
authors: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA.|Departamento de Física, Escuela Politécnica Nacional, Quito, Ecuador.
authors: Leonardo
authors: L
authors: Basile
authors: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA.
authors: Juan-Carlos
authors: JC
authors: Idrobo
authors: Geophysical Laboratory, Carnegie Institution of Washington, Washington, DC, 20015, USA.|European Spallation Source ERIC, S-22100, Lund, Sweden.
authors: Malcolm
authors: M
authors: Guthrie
authors: Center for High Pressure Science and Technology Advanced Research, Beijing, 100094, P.R. China.|HPSynC, Geophysical Laboratory, Carnegie Institution of Washington, Argonne, IL, 60439, USA.|Geophysical Laboratory, Carnegie Institution of Washington, Washington, DC, 20015, USA.
authors: Ho-Kwang
authors: HK
authors: Mao
keywords: C−H activation; acetonitrile; high-pressure polymerization; hydrogen bonding; hydrogen transfer