Is the elusive trioxydehydroethene neutral (O₂C-CO) detectable in the gas phase?

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dc.contributor.authorPeppe, S.
dc.contributor.authorDua, S.
dc.contributor.authorBowie, J.
dc.date.issued2001
dc.descriptionCopyright © 2001 American Chemical Society
dc.description.abstractThe covalently bound radical anion [O<inf>2</inf>C-CO]<sup>-.</sup> is formed when 1,3-dioxolane-2,5-dione captures an electron followed by retro-cleavage of CH<inf>2</inf>O. Calculations at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory indicate that there are a number of neutral isomers with formula C<inf>2</inf>O<inf>3</inf>, viz. van der Waals complex O<inf>2</inf>C- - -CO (rel. energy = 0 kcal mol<sup>-1</sup>), singlet oxiran dione (760.9 kcal mol<sup>-1</sup>), triplet OCOCO (+99.4 kcal mol<sup>-1</sup>), covalently bound triplet O<inf>2</inf>C-CO (+ 107.6 kcal mol<sup>-1</sup>), singlet trioxapropellane (+171.9 kcal mol<sup>-1</sup>) and triplet trioxapropellane (+ 222.4 kcal mol<sup>-1</sup>). Of these, only triplet O<inf>2</inf>C-CO is accessible by vertical Franck-Condon one-electron oxidation of [O<inf>2</inf>C-CO]<sup>-.</sup>. Neutralization reionization experiments of [O<inf>2</inf>C-CO]<sup>-.</sup> (both <sup>-</sup>NR<sup>+</sup> and <sup>-</sup>NR<sup>-</sup>) fail to produce recovery signals corresponding to ionized C<inf>2</inf>O<inf>3</inf>, which means that if neutral C<inf>2</inf>O<inf>3</inf> is stable, the lifetime must be <10<sup>-6</sup> sec. The <sup>-</sup>NR<sup>+</sup> spectrum of [O<inf>2</inf>C-CO]<sup>-.</sup> shows peaks corresponding to CO<sup>+.</sup>, CO<inf>2</inf><sup>+.</sup> and to [O =C = C = O]<sup>+.</sup>. The last of these species can only be formed from a decomposing C<inf>2</inf>O<inf>3</inf><sup>+.</sup> radical cation by a process endothermic by 47 kcal mol<sup>-1</sup> [at the CCSD-(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory]. Calculations at this same level of theory indicate that the vertical one-electron oxidation of [O<inf>2</inf>C-CO]<sup>-.</sup> to triplet O<inf>2</inf>C-CO ground state produces the neutral with essentially no excess energy. There are two dissociation pathways of this triplet neutral, (i) an endothermic process yielding <sup>3</sup>CO + <sup>-</sup>CO<inf>2</inf> (+ 28.9 kcal mol<sup>-1</sup>), and (ii) an exothermic process (-6.8 kcal mol<sup>-1</sup>) with a barrier of 5.4 kcal mol<sup>-1</sup> yielding <sup>1</sup>CO + <sup>3</sup>CO<inf>2</inf>. A combination of experimental and theoretical data, suggests that vertical oxidation of [O<inf>2</inf>C-CO]<sup>-.</sup> produces only one neutral C<inf>2</inf>O<inf>3</inf> isomer; a transient triplet O<inf>2</inf>C-CO neutral whose lifetime is less than 10<sup>-6</sup> sec.
dc.description.statementofresponsibilitySalvatore Peppe, Suresh Dua, and John H. Bowie
dc.identifier.citationJournal of Physical Chemistry A, 2001; 105(44):10139-10145
dc.identifier.doi10.1021/jp012331j
dc.identifier.issn1089-5639
dc.identifier.issn1520-5215
dc.identifier.urihttp://hdl.handle.net/2440/4624
dc.language.isoen
dc.provenanceWeb Release Date: October 6, 2001
dc.publisherAmer Chemical Soc
dc.source.urihttps://doi.org/10.1021/jp012331j
dc.titleIs the elusive trioxydehydroethene neutral (O₂C-CO) detectable in the gas phase?
dc.title.alternativeIs the elusive trioxydehydroethene neutral (O(2)C-CO) detectable in the gas phase?
dc.typeJournal article
pubs.publication-statusPublished

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