Source:http://linkedlifedata.com/resource/pubmed/id/19905019
| Subject | Predicate | Object | Context |
|---|---|---|---|
| pubmed-article:19905019 | rdf:type | pubmed:Citation | lld:pubmed |
| pubmed-article:19905019 | lifeskim:mentions | umls-concept:C0022203 | lld:lifeskim |
| pubmed-article:19905019 | lifeskim:mentions | umls-concept:C1511695 | lld:lifeskim |
| pubmed-article:19905019 | lifeskim:mentions | umls-concept:C2603343 | lld:lifeskim |
| pubmed-article:19905019 | lifeskim:mentions | umls-concept:C0439596 | lld:lifeskim |
| pubmed-article:19905019 | pubmed:issue | 46 | lld:pubmed |
| pubmed-article:19905019 | pubmed:dateCreated | 2009-11-12 | lld:pubmed |
| pubmed-article:19905019 | pubmed:abstractText | 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 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)(+). | lld:pubmed |
| pubmed-article:19905019 | pubmed:language | eng | lld:pubmed |
| pubmed-article:19905019 | pubmed:journal | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:19905019 | pubmed:status | PubMed-not-MEDLINE | lld:pubmed |
| pubmed-article:19905019 | pubmed:month | Nov | lld:pubmed |
| pubmed-article:19905019 | pubmed:issn | 1520-5215 | lld:pubmed |
| pubmed-article:19905019 | pubmed:author | pubmed-author:BowieJohn HJH | lld:pubmed |
| pubmed-article:19905019 | pubmed:author | pubmed-author:BuntineMark... | lld:pubmed |
| pubmed-article:19905019 | pubmed:author | pubmed-author:WangTianfangT | lld:pubmed |
| pubmed-article:19905019 | pubmed:issnType | Electronic | lld:pubmed |
| pubmed-article:19905019 | pubmed:day | 19 | lld:pubmed |
| pubmed-article:19905019 | pubmed:volume | 113 | lld:pubmed |
| pubmed-article:19905019 | pubmed:owner | NLM | lld:pubmed |
| pubmed-article:19905019 | pubmed:authorsComplete | Y | lld:pubmed |
| pubmed-article:19905019 | pubmed:pagination | 12952-60 | lld:pubmed |
| pubmed-article:19905019 | pubmed:year | 2009 | lld:pubmed |
| pubmed-article:19905019 | pubmed:articleTitle | Study of the isomers of isoelectronic C(4), (C(3)B)(-), and (C(3)N)(+): rearrangements through cyclic isomers. | lld:pubmed |
| pubmed-article:19905019 | pubmed:affiliation | Department of Chemistry, The University of Adelaide, South Australia. | lld:pubmed |
| pubmed-article:19905019 | pubmed:publicationType | Journal Article | lld:pubmed |