Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions
- 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.
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.
- Research Organization:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA); National Natural Science Foundation of China (NSFC); National Science Foundation (NSF)
- Grant/Contract Number:
- AC05-00OR22725; SC0001057; NA0002006; U1530402
- OSTI ID:
- 1311293
- Alternate ID(s):
- OSTI ID: 1401702
- Journal Information:
- 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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