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Issue 12, 2001
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The unusual neutral OCOCO and possible charged analogues. A theoretical investigation

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Abstract

Calculations at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31+G(d) level of theory indicate that singlet neutral OCOCO is unstable with respect to dissociation to CO2 and CO. In contrast, triplet OCOCO is a stable species provided it can be formed with excess energy of less than 41 kJ mol−1 [the process 3OCOCO → 1CO + 3CO2 is endothermic by only 9 kJ mol−1, but the barrier for this process is 41 kJ mol−1]. Triplet OCOCO is not accessible by one-electron oxidation from [OCOCO]−˙ or one-electron reduction from [OCOCO]+˙ because neither of these charged species is stable at the level of theory used for these calculations. A report by Cooper and Compton indicates that dissociative electron capture by maleic anhydride results in loss of the elements of C2H2 yielding an anion C2O3˙. Calculations at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31+G(d) level of theory suggests that the ion radical C2O3˙ may be the stable species [O2C–CO]˙ provided that the dissociating maleic anhydride radical anion has excess energy of at least 260 kJ mol−1.

Graphical abstract: The unusual neutral OCOCO and possible charged analogues. A theoretical investigation

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Publication details

The article was received on 17 Sep 2001, accepted on 12 Oct 2001 and first published on 09 Nov 2001


Article type: Paper
DOI: 10.1039/B108425A
Citation: J. Chem. Soc., Perkin Trans. 2, 2001,0, 2244-2247
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    The unusual neutral OCOCO and possible charged analogues. A theoretical investigation

    S. Dua, S. Peppe and J. H. Bowie, J. Chem. Soc., Perkin Trans. 2, 2001, 0, 2244
    DOI: 10.1039/B108425A

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