Understanding the chemical dynamics of the reactions of dicarbon with 1-butyne, 2-butyne, and 1,2-butadiene – toward the formation of resonantly stabilized free radicals
Abstract
In this work, the reaction dynamics of the dicarbon radical C2(a3Πu/X1Σg+) in the singlet and triplet state with C4H6 isomers 2-butyne, 1-butyne and 1,2-butadiene were investigated at collision energies of about 26 kJ mol-1 using the crossed molecular beam technique and supported by ab initio and RRKM calculations. The reactions are all indirect, forming C6H6 complexes through barrierless additions by dicarbon on the triplet and singlet surfaces. Isomerization of the C6H6 reaction intermediate leads to product formation by hydrogen loss in a dicarbon–hydrogen atom exchange mechanism forming acyclic C6H5 reaction products through loose exit transition states in overall exoergic reactions.
- Authors:
-
- Univ. of Hawaii at Manoa, Honolulu, HI (United States)
- Florida International Univ., Miami, FL (United States)
- Publication Date:
- Research Org.:
- Univ. of Hawaii, Honolulu, HI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1603786
- Grant/Contract Number:
- FG02-03ER15411; FG02-04ER15570
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 16; Journal Issue: 24; 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
Parker, Dorian S. N., Maity, Surajit, Dangi, Beni B., Kaiser, Ralf I., Landera, Alexander, and Mebel, Alexander M. Understanding the chemical dynamics of the reactions of dicarbon with 1-butyne, 2-butyne, and 1,2-butadiene – toward the formation of resonantly stabilized free radicals. United States: N. p., 2014.
Web. doi:10.1039/c4cp00639a.
Parker, Dorian S. N., Maity, Surajit, Dangi, Beni B., Kaiser, Ralf I., Landera, Alexander, & Mebel, Alexander M. Understanding the chemical dynamics of the reactions of dicarbon with 1-butyne, 2-butyne, and 1,2-butadiene – toward the formation of resonantly stabilized free radicals. United States. https://doi.org/10.1039/c4cp00639a
Parker, Dorian S. N., Maity, Surajit, Dangi, Beni B., Kaiser, Ralf I., Landera, Alexander, and Mebel, Alexander M. Fri .
"Understanding the chemical dynamics of the reactions of dicarbon with 1-butyne, 2-butyne, and 1,2-butadiene – toward the formation of resonantly stabilized free radicals". United States. https://doi.org/10.1039/c4cp00639a. https://www.osti.gov/servlets/purl/1603786.
@article{osti_1603786,
title = {Understanding the chemical dynamics of the reactions of dicarbon with 1-butyne, 2-butyne, and 1,2-butadiene – toward the formation of resonantly stabilized free radicals},
author = {Parker, Dorian S. N. and Maity, Surajit and Dangi, Beni B. and Kaiser, Ralf I. and Landera, Alexander and Mebel, Alexander M.},
abstractNote = {In this work, the reaction dynamics of the dicarbon radical C2(a3Πu/X1Σg+) in the singlet and triplet state with C4H6 isomers 2-butyne, 1-butyne and 1,2-butadiene were investigated at collision energies of about 26 kJ mol-1 using the crossed molecular beam technique and supported by ab initio and RRKM calculations. The reactions are all indirect, forming C6H6 complexes through barrierless additions by dicarbon on the triplet and singlet surfaces. Isomerization of the C6H6 reaction intermediate leads to product formation by hydrogen loss in a dicarbon–hydrogen atom exchange mechanism forming acyclic C6H5 reaction products through loose exit transition states in overall exoergic reactions.},
doi = {10.1039/c4cp00639a},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 24,
volume = 16,
place = {United States},
year = {Fri May 02 00:00:00 EDT 2014},
month = {Fri May 02 00:00:00 EDT 2014}
}
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