The formation of the neutral isomers NCCCCO and CCC(O)CN in the gas phase from ionic precursors: a joint experimental and theoretical study

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dc.contributor.authorDua, S.
dc.contributor.authorPeppe, S.
dc.contributor.authorBowie, J.
dc.date.issued2002
dc.descriptionCopyright © 2002 American Chemical Society
dc.description.abstractThe 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.
dc.description.statementofresponsibilitySuresh Dua, Salvatore Peppe, and John H. Bowie
dc.identifier.citationJournal of Physical Chemistry A, 2002; 106(43):10470-10476
dc.identifier.doi10.1021/jp020524g
dc.identifier.issn1089-5639
dc.identifier.issn1520-5215
dc.identifier.urihttp://hdl.handle.net/2440/4622
dc.language.isoen
dc.provenanceWeb Release Date: October 8, 2002
dc.publisherAmer Chemical Soc
dc.source.urihttps://doi.org/10.1021/jp020524g
dc.titleThe formation of the neutral isomers NCCCCO and CCC(O)CN in the gas phase from ionic precursors: a joint experimental and theoretical study
dc.typeJournal article
pubs.publication-statusPublished

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