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    Study of the Isomers of Isoelectronic C-4, (C3B)(-), and (C3N)(+): Rearrangements through Cyclic Isomers

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    Fulltext not available
    Authors
    Wang, Tianfang
    Buntine, Mark
    Bowie, John
    Date
    2009
    Type
    Journal Article
    
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    Citation
    Wang, Tianfang and Buntine, Mark and Bowie, John. 2009. Study of the Isomers of Isoelectronic C-4, (C3B)(-), and (C3N)(+): Rearrangements through Cyclic Isomers. Journal of Physical Chemistry A 113 (46): pp. 12952-12960.
    Source Title
    Journal of Physical Chemistry A
    DOI
    10.1021/jp907484z
    ISSN
    10895639
    School
    Department of Chemical Engineering
    URI
    http://hdl.handle.net/20.500.11937/34297
    Collection
    • Curtin Research Publications
    Abstract

    Optimized structures of the isoelectronic cumulenes (CCCB)(-), CCCC, and (CCCN)(+) and of their isomers formed by rearrangement have been calculated at the B3LYP/6-311+ G(3df) level of theory with relative energies and electronic states determined at the CCSD(T)/aug-cc-pVTZ level of theory. The ground states of CCCC and (CCCN)(+) are triplets, whereas the ground state of (CCCB)(-) is a quasi-linear singlet structure that is only 0.6 kcal mol(-1) more negative in energy than the linear triplet. When energized, both triplet and singlet CCCC cyclize to planar rhomboids, of which the singlet is the lowest-energy configuration. Ring-opening of rhomboid C-4 reforms CCCC with the carbons partially randomized. Similar rear-rangements occur for (CCCB)(-) and (CCCN)(+), but the reactions are different in the detail. In the case of (CCCN)(+), rearrangement of atoms is supported both experimentally and theoretically. Because (CCCB)(-) and (CCCN)(+) are not symmetrical, two fully cyclized forms are possible; the one more resembling a rhomboid structure is called a "kite" structure, and the other is called a "fail" structure. The rearrangement of (CCCB)(-) is more favored via the triplet with equilibrating kite and fan structures being formed, whereas the singlet (CCCN)(+) ring closes to give the singlet kite structure, which may ring open to give a mixture of (CCCN)(+) and (CCNC)(+). Intersystem crossing may occur for the triplet and singlet forms of CCCC and (CCCB)(-) but not for (CCCN)(+).

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