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Title: An Experimental and Theoretical Study on the Formation of 2-Methylnaphthalene (C11H10/C11H3D7) in the Reactions of the Para-Tolyl (C7H7) and Para-Tolyl-d7 (C7D7) with Vinylacetylene (C4H4)

Abstract

We introduce for the very first time single collision experimental evidence that a methyl-substituted polycyclic aromatic hydrocarbon (PAH) – 2-methylnaphthalene – can be formed without an entrance barrier via indirect scattering dynamics through a bimolecular collision of two non-PAH reactants: the para-tolyl radical and vinylacetylene. Theory reflects that this reaction is initiated by the addition of the para-tolyl radical to either the terminal acetylene carbon (C4) or a vinyl carbon (C1) leading eventually to two distinct radical intermediates. Importantly, addition at C1 was found to be barrierless via a van-der-Waals complex implying this mechanism can play a key role in forming methyl substituted PAHs in low temperature extreme environments such as the interstellar medium and hydrocarbon-rich atmospheres of planets and their moons in the outer Solar System. Both reaction pathways involve a sequence of isomerizations via hydrogen transfer, ring closure, and ring opening and final hydrogen dissociation through tight exit transition states to form 2-methylnaphthalene in overall exoergic processes. Less favorable pathways leading to monocyclic products are also found. Our report predict that reactions of substituted aromatic radicals can mechanistically deliver odd-numbered PAHs that are formed in significant quantities in the combustion of fossil fuels.

Authors:
 [1];  [1];  [1];  [2];  [3];  [4];  [5];  [5]
+ Show Author Affiliations
  1. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
  2. Emory Univ., Atlanta, GA (United States)
  3. Emory Univ., Atlanta, GA (United States); Russian Academy of Sciences (RAS), St. Petersburg (Russian Federation)
  4. Emory Univ., Atlanta, GA (United States); Kyoto Univ. (Japan)
  5. Ruhr Univ., Bochum (Germany)
Publication Date:
Research Org.:
Univ. of Hawaii, Honolulu, HI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); US Air Force Office of Scientific Research (AFOSR)
OSTI Identifier:
1602781
Grant/Contract Number:  
FG02-03ER15411; FA9550-10-1-0304; FA9550-12-1-0472
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 118; Journal Issue: 15; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Parker, Dorian S. N., Dangi, Beni B., Kaiser, Ralf I., Jamal, Adeel, Ryazantsev, Mikhail N., Morokuma, Keiji, Korte, André, and Sander, Wolfram. An Experimental and Theoretical Study on the Formation of 2-Methylnaphthalene (C11H10/C11H3D7) in the Reactions of the Para-Tolyl (C7H7) and Para-Tolyl-d7 (C7D7) with Vinylacetylene (C4H4). United States: N. p., 2014. Web. doi:10.1021/jp501210d.
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Parker, Dorian S. N., Dangi, Beni B., Kaiser, Ralf I., Jamal, Adeel, Ryazantsev, Mikhail N., Morokuma, Keiji, Korte, André, & Sander, Wolfram. An Experimental and Theoretical Study on the Formation of 2-Methylnaphthalene (C11H10/C11H3D7) in the Reactions of the Para-Tolyl (C7H7) and Para-Tolyl-d7 (C7D7) with Vinylacetylene (C4H4). United States. https://doi.org/10.1021/jp501210d
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Parker, Dorian S. N., Dangi, Beni B., Kaiser, Ralf I., Jamal, Adeel, Ryazantsev, Mikhail N., Morokuma, Keiji, Korte, André, and Sander, Wolfram. Wed . "An Experimental and Theoretical Study on the Formation of 2-Methylnaphthalene (C11H10/C11H3D7) in the Reactions of the Para-Tolyl (C7H7) and Para-Tolyl-d7 (C7D7) with Vinylacetylene (C4H4)". United States. https://doi.org/10.1021/jp501210d. https://www.osti.gov/servlets/purl/1602781.
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@article{osti_1602781,
title = {An Experimental and Theoretical Study on the Formation of 2-Methylnaphthalene (C11H10/C11H3D7) in the Reactions of the Para-Tolyl (C7H7) and Para-Tolyl-d7 (C7D7) with Vinylacetylene (C4H4)},
author = {Parker, Dorian S. N. and Dangi, Beni B. and Kaiser, Ralf I. and Jamal, Adeel and Ryazantsev, Mikhail N. and Morokuma, Keiji and Korte, André and Sander, Wolfram},
abstractNote = {We introduce for the very first time single collision experimental evidence that a methyl-substituted polycyclic aromatic hydrocarbon (PAH) – 2-methylnaphthalene – can be formed without an entrance barrier via indirect scattering dynamics through a bimolecular collision of two non-PAH reactants: the para-tolyl radical and vinylacetylene. Theory reflects that this reaction is initiated by the addition of the para-tolyl radical to either the terminal acetylene carbon (C4) or a vinyl carbon (C1) leading eventually to two distinct radical intermediates. Importantly, addition at C1 was found to be barrierless via a van-der-Waals complex implying this mechanism can play a key role in forming methyl substituted PAHs in low temperature extreme environments such as the interstellar medium and hydrocarbon-rich atmospheres of planets and their moons in the outer Solar System. Both reaction pathways involve a sequence of isomerizations via hydrogen transfer, ring closure, and ring opening and final hydrogen dissociation through tight exit transition states to form 2-methylnaphthalene in overall exoergic processes. Less favorable pathways leading to monocyclic products are also found. Our report predict that reactions of substituted aromatic radicals can mechanistically deliver odd-numbered PAHs that are formed in significant quantities in the combustion of fossil fuels.},
doi = {10.1021/jp501210d},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 15,
volume = 118,
place = {United States},
year = {Wed Mar 19 00:00:00 EDT 2014},
month = {Wed Mar 19 00:00:00 EDT 2014}
}
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    Works referencing / citing this record:

    Formation of bicyclic polycyclic aromatic hydrocarbons (PAHs) from the reaction of a phenyl radical with cis -3-penten-1-yne
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    Reactivity of the Indenyl Radical (C 9 H 7 ) with Acetylene (C 2 H 2 ) and Vinylacetylene (C 4 H 4 )
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