Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH 3 to CN under Extreme Conditions

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, Juan‐Carlos; Guthrie, Malcolm; Mao, Ho‐kwang

doi:10.1002/ange.201606198

Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH ₃ to CN under Extreme Conditions

Journal Article · Thu Aug 25 00:00:00 EDT 2016 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201606198· OSTI ID:1401008

Zheng, Haiyan ^[1]; Li, Kuo ^[2]; Cody, George D. ^[3]; Tulk, Christopher A. ^[4]; Dong, Xiao ^[1]; Gao, Guoying ^[5]; Molaison, Jamie J. ^[4]; Liu, Zhenxian ^[3]; Feygenson, Mikhail ^[6]; Yang, Wenge ^[7]; Ivanov, Ilia N. ^[8]; Basile, Leonardo ^[9]; Idrobo, Juan‐Carlos ^[8]; Guthrie, Malcolm ^[10]; Mao, Ho‐kwang ^[11]

Center for High Pressure Science and Technology Advanced Research Beijing 100094 P.R. China
Center for High Pressure Science and Technology Advanced Research Beijing 100094 P.R. China, Geophysical Laboratory Carnegie Institution of Washington Washington DC 20015 USA
Geophysical Laboratory Carnegie Institution of Washington Washington DC 20015 USA
Neutron Sciences Directorate Oak Ridge National Laboratory Oak Ridge TN 37831 USA
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
Neutron Sciences Directorate Oak Ridge National Laboratory Oak Ridge TN 37831 USA, Jülich Center for Neutron Science Forschungszentrum Jülich GmbH D-52425 Jülich Germany
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
Center for Nanophase Materials Sciences Oak Ridge National Laboratory Oak Ridge TN 37831 USA
Center for Nanophase Materials Sciences Oak Ridge National Laboratory Oak Ridge TN 37831 USA, Departamento de Física Escuela Politécnica Nacional Quito Ecuador
Geophysical Laboratory Carnegie Institution of Washington Washington DC 20015 USA, European Spallation Source ERIC S-22100 Lund Sweden
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

Abstract

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.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0001057

OSTI ID:: 1401008

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 39 Vol. 128; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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

Journal Article · Thu Aug 25 00:00:00 EDT 2016 · Angewandte Chemie International Edition (Online) · OSTI ID:1311293

Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH 3 to CN under Extreme Conditions

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Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH ₃ to CN under Extreme Conditions