Please use this identifier to cite or link to this item: https://hdl.handle.net/2440/57078
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Type: Journal article
Title: Study of the isomers of isoelectronic C₄, (C₃B)⁻, and (C₃N)⁺: rearrangements through cyclic isomers
Other Titles: Study of the isomers of isoelectronic C(4), (C(3)B)(-), and (C(3)N)(+): rearrangements through cyclic isomers
Author: Wang, T.
Buntine, M.
Bowie, J.
Citation: The Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory, 2009; 113(46):12952-12960
Publisher: Amer Chemical Soc
Issue Date: 2009
ISSN: 1089-5639
1520-5215
Statement of
Responsibility: 
Tianfang Wang, Mark A. Buntine and John H. Bowie
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 C₄ reforms CCCC with the carbons partially randomized. Similar rearrangements 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 “fan” 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)+.
DOI: 10.1021/jp907484z
Grant ID: ARC
Published version: http://dx.doi.org/10.1021/jp907484z
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