Journal article
Study of the Isomers of Isoelectronic C4, (C3B)−, and (C3N)+: Rearrangements through Cyclic Isomers
Journal of Physical Chemistry Part A, Vol.113(46), pp.12952-12960
2009
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)+.
Details
- Title
- Study of the Isomers of Isoelectronic C4, (C3B)−, and (C3N)+: Rearrangements through Cyclic Isomers
- Authors
- Tianfang Wang (Author) - University of AdelaideM A Buntine (Author) - Curtin UniversityJ H Bowie (Author) - University of Adelaide
- Publication details
- Journal of Physical Chemistry Part A, Vol.113(46), pp.12952-12960
- Publisher
- American Chemical Society
- Date published
- 2009
- DOI
- 10.1021/jp907484z
- ISSN
- 1089-5639
- Organisation Unit
- School of Science and Engineering - Legacy; University of the Sunshine Coast, Queensland; School of Science, Technology and Engineering; Centre for Bioinnovation
- Language
- English
- Record Identifier
- 99450394402621
- Output Type
- Journal article
Metrics
1 File views/ downloads
352 Record Views
InCites Highlights
These are selected metrics from InCites Benchmarking & Analytics tool, related to this output
- Collaboration types
- Domestic collaboration
- Web Of Science research areas
- Chemistry, Physical
- Physics, Atomic, Molecular & Chemical