dc.contributor.author | Nicolaïdes, Andrew N. | en |
dc.creator | Nicolaïdes, Andrew N. | en |
dc.date.accessioned | 2019-11-21T06:21:41Z | |
dc.date.available | 2019-11-21T06:21:41Z | |
dc.date.issued | 2003 | |
dc.identifier.uri | http://gnosis.library.ucy.ac.cy/handle/7/55894 | |
dc.description.abstract | A prerequisite for a stable singlet hydrocarbon carbene is the existence of high barriers toward isomerization. Four derivatives of cyclopentylidene (1-4) with rigid and varying carbon cages are examined computationally at the B3LYP/6-311+G(d,p) level of theory. Singlet ground states are predicted for carbenes 1-4, with ΔE ST's = 7-22 kcal/mol. The rearrangement paths considered are 1,3-hydrogen shift, 1,2-carbon shift and β-CC bond-cleavage. Carbenes 3 and 4 lie in relatively shallow potential-energy wells (around 4 and 6 kcal/mol, respectively) and are expected to rearrange via 1,3-hydrogen shifts to cyclopropane derivatives. For 1 and 2, the lowest energy rearrangement path is β-CC bond-cleavage requiring about 12 and 20 kcal/mol, respectively, placing 2 in the deepest potential-energy well among the four carbenes. | en |
dc.source | Journal of the American Chemical Society | en |
dc.source.uri | https://www.scopus.com/inward/record.uri?eid=2-s2.0-0042868658&doi=10.1021%2fja0299699&partnerID=40&md5=517cd860d40eb1c7a1fc3c1586444b27 | |
dc.subject | article | en |
dc.subject | kinetics | en |
dc.subject | energy | en |
dc.subject | Hydrogen | en |
dc.subject | chemical structure | en |
dc.subject | geometry | en |
dc.subject | isomerism | en |
dc.subject | Nitrogen compounds | en |
dc.subject | Ground state | en |
dc.subject | Chemical bonds | en |
dc.subject | Isomerization | en |
dc.subject | carbene | en |
dc.subject | vibration | en |
dc.subject | Bond cleavage | en |
dc.subject | hydrocarbon | en |
dc.title | Singlet hydrocarbon carbenes with high barriers toward isomerization: A computational investigation | en |
dc.type | info:eu-repo/semantics/article | |
dc.identifier.doi | 10.1021/ja0299699 | |
dc.description.volume | 125 | |
dc.description.issue | 30 | |
dc.description.startingpage | 9070 | |
dc.description.endingpage | 9073 | |
dc.author.faculty | 002 Σχολή Θετικών και Εφαρμοσμένων Επιστημών / Faculty of Pure and Applied Sciences | |
dc.author.department | Τμήμα Χημείας / Department of Chemistry | |
dc.type.uhtype | Article | en |
dc.description.notes | <p>Cited By :7</p> | en |
dc.source.abbreviation | J.Am.Chem.Soc. | en |