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

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 100094 P.R. China
  2. Center for High Pressure Science and Technology Advanced Research, Beijing 100094 P.R. China; Geophysical Laboratory, Carnegie Institution of Washington, Washington DC 20015 USA
  3. Geophysical Laboratory, Carnegie Institution of Washington, Washington DC 20015 USA
  4. Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA
  5. 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
  6. Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA; Jülich Center for Neutron Science, Forschungszentrum Jülich GmbH, D-52425 Jülich Germany
  7. 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
  8. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA
  9. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA; Departamento de Física, Escuela Politécnica Nacional, Quito Ecuador
  10. Geophysical Laboratory, Carnegie Institution of Washington, Washington DC 20015 USA; European Spallation Source ERIC, S-22100 Lund Sweden
  11. 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
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1354484
Report Number(s):
BNL-113001-2016-JA
Journal ID: ISSN 1433-7851
DOE Contract Number:
SC00112704
Resource Type:
Journal Article
Resource Relation:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 55; Journal Issue: 39
Country of Publication:
United States
Language:
English

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 CH 3 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 CH 3 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. 2016. "Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH 3 to CN under Extreme Conditions". United States. doi:10.1002/anie.201606198.
@article{osti_1354484,
title = {Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH 3 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 = {},
doi = {10.1002/anie.201606198},
journal = {Angewandte Chemie (International Edition)},
number = 39,
volume = 55,
place = {United States},
year = 2016,
month = 8
}
  • 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 spmore » 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.« less
  • Cited by 4
  • The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH{sub 3}CN (1) and its isotopic variants, OH + CD{sub 3}CN (2), OD + CH{sub 3}CN (3), and OD + CD{sub 3}CN (4). Reactions 1 and 2 were studied as a function of pressure and temperature in N{sub 2}, N{sub 2}/O{sub 2}, and He buffer gases. In the absence of O{sub 2} all four reactions displayed well-behaved kinetics with exponential OH decays and pseudo-firt-order rate constants which were proportional to substrate concentration. Data obtained in N{sub 2} over themore » range 50-700 Torr at 298 K are consistent with k{sub 1} showing a small pressure dependence. The Arrhenius expression obtained by averaging data at all pressures is k{sub 1}(T) = (1.1{sub {minus}0.3}{sup +0.5}) {times} 10{sup {minus}12} exp(({minus}1,130 {plus minus} 90)/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The kinetics of reaction 2 are found to be pressure dependent with k{sub 2} (298 K) increasing from (1.21 {plus minus} 0.12) {times} 10{sup {minus}14} to (2.16 {plus minus} 0.11) {times} 10{sup {minus}14} cm{sup 3} molecule{sup {minus}1}s{sup {minus}1} over the pressure range 50-700 Torr of N{sub 2} at 298 K. Data at pressures >600 Torr give k{sub 2}(T) = (9.4{sub {minus}5.0}{sup +13.4}) {times} 10{sup {minus}13} exp(({minus}1,180 {plus minus} 250)/T) cm{sup 3} molecule{sup {minus}1}s{sup {minus}1}.« less