The formation of the neutral isomers NCCCCO and CCC(O)CN in the gas phase from ionic precursors: a joint experimental and theoretical study
Date
2002
Authors
Dua, S.
Peppe, S.
Bowie, J.
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Journal article
Citation
Journal of Physical Chemistry A, 2002; 106(43):10470-10476
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Suresh Dua, Salvatore Peppe, and John H. Bowie
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Abstract
The two neutral radicals NCCCCO and CCC(O)CN have been made by collision-induced vertical one-electron reduction and oxidation (respectively) of the charged species NCCCCO<sup>+</sup> and <sup>-</sup> CCC(O)CN. The two charged precursors were prepared by the following reactions: (a) [NC-C≡C-CO-CH<inf>3</inf>]<sup>+.</sup> → NCCCO<sup>+</sup> + CH<inf>3</inf><sup>.</sup> and (b) (CH<inf>3</inf>)<inf>3</inf>Si-C≡C-CO-CN + F<sup>-</sup> → n <sup>-</sup>CCC(O)CN + (CH<inf>3</inf>)<inf>3</inf>SiF. Neutral NCCCCO is a stable species, but when energized decomposes by loss of CO to form the radical CCCN [process endothermic by 38.5 kcal mol<sup>-1</sup>: calculations at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory]. Neutral CCC(O)CN is 46.8 kcal mol<sup>-1</sup> more positive in energy than the isomer NCCCCO. When energized, CCC(O)CN decomposes by loss of NC to form CCCO (process endothermic by 28.1 kcal mol<sup>-1</sup>), but also undergoes a rearrangement process to produce NCCCCO, which is formed with excess energy and may decompose by loss of CO.
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Dissertation Note
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Web Release Date: October 8, 2002
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Copyright © 2002 American Chemical Society