Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 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/anie.201606198

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)

DOI:https://doi.org/10.1002/anie.201606198· OSTI ID:1311293

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 (China)
Center for High Pressure Science and Technology Advanced Research, Beijing (China) ; Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.
Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Cornell Univ., Ithaca, NY (United States); Yanshan University State Key Laboratory of Metastable Materials Science and Technology, Qinhuangdao (China)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Julich Research Centre (Germany). Julich Centre for Neutron Science (JCNS)
Center for High Pressure Science and Technology Advanced Research, Beijing (China); Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); National Polytechnic School, Quito (Ecuador)
Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.; European Spallation Source ERIC, Lund (Sweden)
Center for High Pressure Science and Technology Advanced Research, Beijing (China); Carnegie Inst. of Washington, Argonne, IL (United States). Geophysical Lab.; Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.

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. In this study, 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. Lastly, 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 (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Spallation Neutron Source (SNS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA); National Natural Science Foundation of China (NSFC); National Science Foundation (NSF)

Grant/Contract Number:: AC05-00OR22725; SC0001057; NA0002006

OSTI ID:: 1311293

Alternate ID(s):: OSTI ID: 1401702
OSTI ID: 1354484
OSTI ID: 1388073

Journal Information:: Angewandte Chemie International Edition (Online), Journal Name: Angewandte Chemie International Edition (Online) Vol. 55; ISSN 1521-3773

Publisher:: Gesselschaft Deutscher ChemikerCopyright Statement

Country of Publication:: United States

Language:: English

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A step toward better understanding of behavior of organic materials at simultaneous high pressures and high temperatures Chertkova, N.; Ohfuji, H.; Nomura, R. High Pressure Research, Vol. 38, Issue 3 https://doi.org/10.1080/08957959.2018.1476506	journal	May 2018
From Molecules to Carbon Materials—High Pressure Induced Polymerization and Bonding Mechanisms of Unsaturated Compounds Yang, Xin; Wang, Xuan; Wang, Yida Crystals, Vol. 9, Issue 10 https://doi.org/10.3390/cryst9100490	journal	September 2019

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