Gas-Phase Synthesis of the Elusive Cyclooctatetraenyl Radical (C 8H7) via Triplet Aromatic Cyclooctatetraene (C8H8) and Non-Aromatic Cyclooctatriene (C8H8) Intermediates
Abstract
The 1,2,4,7-cyclooctatetraenyl radical (C8H7) has been synthesized for the very first time via the bimolecular gas-phase reaction of ground-state carbon atoms with 1,3,5-cycloheptatriene (C7H8) on the triplet surface under single-collision conditions. The barrierless route to the cyclic 1,2,4,7-cyclooctatetraenyl radical accesses exotic reaction intermediates on the triplet surface, which cannot be synthesized via classical organic chemistry methods: the triplet non-aromatic 2,4,6-cyclooctatriene (C8H8) and the triplet aromatic 1,3,5,7-cyclooctatetraene (C8H8). In this study, our approach provides a clean gas-phase synthesis of this hitherto elusive cyclic radical species 1,2,4,7-cyclooctatetraenyl via a single-collision event and opens up a versatile, unconventional path to access this previously largely obscure class of cyclooctatetraenyl radicals, which have been impossible to access through classical synthetic methods.
- Authors:
-
[1];
- Univ. of Hawaii at Manoa, Honolulu, HI (United States)
- Dongguk Univ., Seoul (Korea, Republic of)
- Florida International Univ., Miami, FL (United States); Samara National Research Univ. (Russia)
- Publication Date:
- Research Org.:
- Univ. of Hawaii, Honolulu, HI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Ministry of Education and Science of the Russian Federation
- OSTI Identifier:
- 1602965
- Alternate Identifier(s):
- OSTI ID: 1394005
- Grant/Contract Number:
- FG02-03ER15411; FG02‐04ER15570; 14.Y26.31.0020; FG02-04ER15570
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 44; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; gas-phase chemistry; mass spectrometry; reaction dynamics; reaction intermediates; single-collision conditions
Citation Formats
Lucas, Michael, Thomas, Aaron M., Zhao, Long, Kaiser, Ralf I., Kim, Gap-Sue, and Mebel, Alexander M. Gas-Phase Synthesis of the Elusive Cyclooctatetraenyl Radical (C 8H7) via Triplet Aromatic Cyclooctatetraene (C8H8) and Non-Aromatic Cyclooctatriene (C8H8) Intermediates. United States: N. p., 2017.
Web. doi:10.1002/anie.201706861.
Lucas, Michael, Thomas, Aaron M., Zhao, Long, Kaiser, Ralf I., Kim, Gap-Sue, & Mebel, Alexander M. Gas-Phase Synthesis of the Elusive Cyclooctatetraenyl Radical (C 8H7) via Triplet Aromatic Cyclooctatetraene (C8H8) and Non-Aromatic Cyclooctatriene (C8H8) Intermediates. United States. https://doi.org/10.1002/anie.201706861
Lucas, Michael, Thomas, Aaron M., Zhao, Long, Kaiser, Ralf I., Kim, Gap-Sue, and Mebel, Alexander M. Fri .
"Gas-Phase Synthesis of the Elusive Cyclooctatetraenyl Radical (C 8H7) via Triplet Aromatic Cyclooctatetraene (C8H8) and Non-Aromatic Cyclooctatriene (C8H8) Intermediates". United States. https://doi.org/10.1002/anie.201706861. https://www.osti.gov/servlets/purl/1602965.
@article{osti_1602965,
title = {Gas-Phase Synthesis of the Elusive Cyclooctatetraenyl Radical (C 8H7) via Triplet Aromatic Cyclooctatetraene (C8H8) and Non-Aromatic Cyclooctatriene (C8H8) Intermediates},
author = {Lucas, Michael and Thomas, Aaron M. and Zhao, Long and Kaiser, Ralf I. and Kim, Gap-Sue and Mebel, Alexander M.},
abstractNote = {The 1,2,4,7-cyclooctatetraenyl radical (C8H7) has been synthesized for the very first time via the bimolecular gas-phase reaction of ground-state carbon atoms with 1,3,5-cycloheptatriene (C7H8) on the triplet surface under single-collision conditions. The barrierless route to the cyclic 1,2,4,7-cyclooctatetraenyl radical accesses exotic reaction intermediates on the triplet surface, which cannot be synthesized via classical organic chemistry methods: the triplet non-aromatic 2,4,6-cyclooctatriene (C8H8) and the triplet aromatic 1,3,5,7-cyclooctatetraene (C8H8). In this study, our approach provides a clean gas-phase synthesis of this hitherto elusive cyclic radical species 1,2,4,7-cyclooctatetraenyl via a single-collision event and opens up a versatile, unconventional path to access this previously largely obscure class of cyclooctatetraenyl radicals, which have been impossible to access through classical synthetic methods.},
doi = {10.1002/anie.201706861},
journal = {Angewandte Chemie (International Edition)},
number = 44,
volume = 56,
place = {United States},
year = {Fri Sep 08 00:00:00 EDT 2017},
month = {Fri Sep 08 00:00:00 EDT 2017}
}
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