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

Abstract

Acetonitrile (CH 3CN) 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 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. 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.

Authors:
 [1];  [2];  [3];  [4];  [1];  [5];  [4];  [3];  [6];  [7];  [8];  [9];  [8];  [10];  [11]
  1. Center for High Pressure Science and Technology Advanced Research, Beijing (China)
  2. Center for High Pressure Science and Technology Advanced Research, Beijing (China) ; Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.
  3. Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  5. Cornell Univ., Ithaca, NY (United States); Yanshan University State Key Laboratory of Metastable Materials Science and Technology, Qinhuangdao (China)
  6. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Julich Research Centre (Germany). Julich Centre for Neutron Science (JCNS)
  7. Center for High Pressure Science and Technology Advanced Research, Beijing (China); Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.
  8. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  9. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); National Polytechnic School, Quito (Ecuador)
  10. Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.; European Spallation Source ERIC, Lund (Sweden)
  11. 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.
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA); National Natural Science Foundation of China (NNSFC); National Science Foundation (NSF)
OSTI Identifier:
1311293
Alternate Identifier(s):
OSTI ID: 1401702
Grant/Contract Number:  
AC05-00OR22725; SC0001057; NA0002006; U1530402
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Angewandte Chemie International Edition (Online)
Additional Journal Information:
Journal Name: Angewandte Chemie International Edition (Online); Journal Volume: 55; Journal ID: ISSN 1521-3773
Publisher:
Gesselschaft Deutscher Chemiker
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

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, and Mao, Ho-kwang. Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions. United States: N. p., 2016. Web. doi:10.1002/anie.201606198.
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. Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions. United States. doi:10.1002/anie.201606198.
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, and Mao, Ho-kwang. Thu . "Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions". United States. doi:10.1002/anie.201606198. https://www.osti.gov/servlets/purl/1311293.
@article{osti_1311293,
title = {Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions},
author = {Zheng, Haiyan and Li, Kuo and Cody, George D. and Tulk, Christopher A. and Dong, Xiao and Gao, Guoying and Molaison, Jamie J. and Liu, Zhenxian and Feygenson, Mikhail and Yang, Wenge and Ivanov, Ilia N. and Basile, Leonardo and Idrobo, Juan-Carlos and Guthrie, Malcolm and Mao, Ho-kwang},
abstractNote = {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.},
doi = {10.1002/anie.201606198},
journal = {Angewandte Chemie International Edition (Online)},
number = ,
volume = 55,
place = {United States},
year = {Thu Aug 25 00:00:00 EDT 2016},
month = {Thu Aug 25 00:00:00 EDT 2016}
}

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