Gas phase formation of cyclopentanaphthalene (benzindene) isomers via reactions of 5- and 6-indenyl radicals with vinylacetylene
Abstract
The tricyclic polycyclic aromatic hydrocarbons (PAHs) 3H-cyclopenta[a]naphthalene (C13H10), 1H-cyclopenta[b]naphthalene (C13H10) and 1H-cyclopenta[a]naphthalene (C13H10) along with their indene-based bicyclic isomers (E)-5-(but-1-en-3-yn-1-yl)-1H-indene, (E)-6-(but-1-en-3-yn-1-yl)-1H-indene, 5-(but-3-ene-1-yn-1-yl)-1H-in-dene, and 6-(but-3-ene-1-yn-1-yl)-1H-indene were formed via a “directed synthesis” in a high-temperature chemical micro reactor at the temperature of 1300 ± 10 K through the reactions of the 5- and 6-indenyl radicals (C9H7˙) with vinylacetylene (C4H4). The isomer distributions were probed utilizing tunable vacuum ultraviolet light by recording the photoionization efficiency curves at mass-to-charge of m/z = 166 (C13H10) and 167 (13CC12H10) of the products in a supersonic molecular beam. Here, the underlying reaction mechanisms involve the initial formation of van-der-Waals complexes followed by addition of the 5- and 6-indenyl radicals to vinylacetylene via submerged barriers, followed by isomerization (hydrogen shifts, ring closures), and termination via atomic hydrogen elimination accompanied by aromatization. All the barriers involved in the formation of 3H-cyclopenta[a]naphthalene, 1H-cyclopenta[b]naphthalene and 1H-cyclopenta[a]naphthalene are submerged with respect to the reactants indicating that the mechanisms are in fact barrierless, potentially forming PAHs via the hydrogen abstraction – vinylacetylene addition (HAVA) pathway in the cold molecular clouds such as Taurus Molecular Cloud-1 (TMC-1) at temperatures as low as 10 K.
- Authors:
-
[1];
[2];
[2];
[2];
[5];
[6];
- Univ. of Hawaii at Manoa, Honolulu, HI (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Samara National Research Univ. (Russia)
- Samara National Research Univ. (Russia); Lebedev Physical Inst., Samara (Russia)
- Samara National Research Univ. (Russia); Florida International Univ., Miami, FL (United States)
- Florida International Univ., Miami, FL (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1814910
- Alternate Identifier(s):
- OSTI ID: 1669154
- Grant/Contract Number:
- AC02-05CH11231; FG02-03ER15411; FG02-04ER15570
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 22; Journal Issue: 39; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Zhao, Long, Kaiser, Ralf I., Lu, Wenchao, Kostko, Oleg, Ahmed, Musahid, Evseev, Mikhail M., Bashkirov, Eugene K., Oleinikov, Artem D., Azyazov, Valeriy N., Mebel, Alexander M., Howlader, A. Hasan, and Wnuk, Stanislaw F. Gas phase formation of cyclopentanaphthalene (benzindene) isomers via reactions of 5- and 6-indenyl radicals with vinylacetylene. United States: N. p., 2020.
Web. doi:10.1039/d0cp03846f.
Zhao, Long, Kaiser, Ralf I., Lu, Wenchao, Kostko, Oleg, Ahmed, Musahid, Evseev, Mikhail M., Bashkirov, Eugene K., Oleinikov, Artem D., Azyazov, Valeriy N., Mebel, Alexander M., Howlader, A. Hasan, & Wnuk, Stanislaw F. Gas phase formation of cyclopentanaphthalene (benzindene) isomers via reactions of 5- and 6-indenyl radicals with vinylacetylene. United States. https://doi.org/10.1039/d0cp03846f
Zhao, Long, Kaiser, Ralf I., Lu, Wenchao, Kostko, Oleg, Ahmed, Musahid, Evseev, Mikhail M., Bashkirov, Eugene K., Oleinikov, Artem D., Azyazov, Valeriy N., Mebel, Alexander M., Howlader, A. Hasan, and Wnuk, Stanislaw F. Thu .
"Gas phase formation of cyclopentanaphthalene (benzindene) isomers via reactions of 5- and 6-indenyl radicals with vinylacetylene". United States. https://doi.org/10.1039/d0cp03846f. https://www.osti.gov/servlets/purl/1814910.
@article{osti_1814910,
title = {Gas phase formation of cyclopentanaphthalene (benzindene) isomers via reactions of 5- and 6-indenyl radicals with vinylacetylene},
author = {Zhao, Long and Kaiser, Ralf I. and Lu, Wenchao and Kostko, Oleg and Ahmed, Musahid and Evseev, Mikhail M. and Bashkirov, Eugene K. and Oleinikov, Artem D. and Azyazov, Valeriy N. and Mebel, Alexander M. and Howlader, A. Hasan and Wnuk, Stanislaw F.},
abstractNote = {The tricyclic polycyclic aromatic hydrocarbons (PAHs) 3H-cyclopenta[a]naphthalene (C13H10), 1H-cyclopenta[b]naphthalene (C13H10) and 1H-cyclopenta[a]naphthalene (C13H10) along with their indene-based bicyclic isomers (E)-5-(but-1-en-3-yn-1-yl)-1H-indene, (E)-6-(but-1-en-3-yn-1-yl)-1H-indene, 5-(but-3-ene-1-yn-1-yl)-1H-in-dene, and 6-(but-3-ene-1-yn-1-yl)-1H-indene were formed via a “directed synthesis” in a high-temperature chemical micro reactor at the temperature of 1300 ± 10 K through the reactions of the 5- and 6-indenyl radicals (C9H7˙) with vinylacetylene (C4H4). The isomer distributions were probed utilizing tunable vacuum ultraviolet light by recording the photoionization efficiency curves at mass-to-charge of m/z = 166 (C13H10) and 167 (13CC12H10) of the products in a supersonic molecular beam. Here, the underlying reaction mechanisms involve the initial formation of van-der-Waals complexes followed by addition of the 5- and 6-indenyl radicals to vinylacetylene via submerged barriers, followed by isomerization (hydrogen shifts, ring closures), and termination via atomic hydrogen elimination accompanied by aromatization. All the barriers involved in the formation of 3H-cyclopenta[a]naphthalene, 1H-cyclopenta[b]naphthalene and 1H-cyclopenta[a]naphthalene are submerged with respect to the reactants indicating that the mechanisms are in fact barrierless, potentially forming PAHs via the hydrogen abstraction – vinylacetylene addition (HAVA) pathway in the cold molecular clouds such as Taurus Molecular Cloud-1 (TMC-1) at temperatures as low as 10 K.},
doi = {10.1039/d0cp03846f},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 39,
volume = 22,
place = {United States},
year = {Thu Sep 24 00:00:00 EDT 2020},
month = {Thu Sep 24 00:00:00 EDT 2020}
}
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