Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3to CN under Extreme Conditions

Haiyan Zheng, Kuo Li, George D. Cody, Christopher A. Tulk, Xiao Dong, Guoying Gao, Jamie J. Molaison, Zhenxian Liu, Mikhail Feygenson, Wenge Yang, Ilia N. Ivanov, Leonardo Basile, Juan Carlos Idrobo, Malcolm Guthrie, Ho Kwang Mao

Research output: Contribution to journalArticlepeer-review

29 Scopus citations

Abstract

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. 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 CH3to 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 sp2and sp3bonded 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.

Original languageEnglish
Pages (from-to)12040-12044
Number of pages5
JournalAngewandte Chemie - International Edition
Volume55
Issue number39
DOIs
StatePublished - Sep 19 2016

Funding

The authors acknowledge the support of NSAF (Grant No:U1530402) and National Natural Science Foundation of China (NSFC) (Grant No: 21501162). This work was partially supported as part of the Energy Frontier Research in Extreme Environment Center (Efree), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under grant number DE-SC0001057, the National Secretariat of Higher Education, Science, Technology and Innovation of Ecuador (SENESCYT). The research at Oak Ridge National Lab's Spallation Neutron Source and Center for Nanophase Materials Sciences was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. The use of beamline U2A was supported by NSF (EAR 1606856, COMPRES) and DOE/NNSA (DE-NA-0002006, CDAC). The authors thank Dr. Roald Hoffmann for his valuable comments and the help in our calculation work.

Keywords

  • C−H activation
  • acetonitrile
  • high-pressure polymerization
  • hydrogen bonding
  • hydrogen transfer

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