o-Phenylene halocarbenonitrenes and o-phenylene chlorocarbenocarbene: A combined experimental and computational approach
dc.contributor.author | Enyo, T. | en |
dc.contributor.author | Arai, N. | en |
dc.contributor.author | Nakane, N. | en |
dc.contributor.author | Nicolaïdes, Andrew N. | en |
dc.contributor.author | Tomioka, H. | en |
dc.creator | Enyo, T. | en |
dc.creator | Arai, N. | en |
dc.creator | Nakane, N. | en |
dc.creator | Nicolaïdes, Andrew N. | en |
dc.creator | Tomioka, H. | en |
dc.date.accessioned | 2019-11-21T06:19:00Z | |
dc.date.available | 2019-11-21T06:19:00Z | |
dc.date.issued | 2005 | |
dc.identifier.uri | http://gnosis.library.ucy.ac.cy/handle/7/55472 | |
dc.description.abstract | Computations find that o-phenylene(halo)carbenonitrenes 2-XN, X = F, Cl, Br, have quinoidal singlet biradical ground states such as the parent o-phenylenecarbenonitrene (2-HN). Compared to the parent 2-HN, halogen substitution stabilizes the A″ states relative to the A′ ones. Halogen substitution also affects the barrier and exothermicity of the ring-opening reaction (to form unsaturated nitriles 4-XN, X = F, Cl, Br), but it has a smaller effect on the ring-closing reaction (to form benzo(aza) cyclobutadiene 3-XN, X = F, Cl, Br). Attempts to generate and observe the o-phenylene(halo)carbenonitrenes 2-XN, X = F, Cl, Br, using matrix isolation spectroscopy under conditions similar to those of the successful observation of 2-HN failed. Instead, the observed photoproducts were a mixture of 3-XN and 4-XN. In each case, the major product of the mixture appears to be the thermodynamically more stable one. In the case of X = Br, the observed mixture contains an additional component that is postulated to be Z-6-BrN. o-Phenylenechlorocarbenocarbene is also computed to have a quinoidal singlet biradical ground state and relatively stabilized A″ excited states. Attempts to generate the biscarbene under matrix isolation conditions led to the detection of benzochlorocyclobutadiene (3-ClC), small amounts of the ring-open product (dienediyne 4-ClC), and cycloalkyne 5-ClC. Computations suggest that the formation of 5-ClC implies the generation of Z-6-ClC, which is analogous to the formation of Z-6-BrN from 2-BrN. © 2005 American Chemical Society. | en |
dc.source | Journal of Organic Chemistry | en |
dc.source.uri | https://www.scopus.com/inward/record.uri?eid=2-s2.0-24944531310&doi=10.1021%2fjo0512204&partnerID=40&md5=c571baad4fa198792810b72654e4eb93 | |
dc.subject | article | en |
dc.subject | Computational methods | en |
dc.subject | unclassified drug | en |
dc.subject | chlorine | en |
dc.subject | thermodynamics | en |
dc.subject | calculation | en |
dc.subject | Substitution reactions | en |
dc.subject | spectroscopy | en |
dc.subject | Spectroscopic analysis | en |
dc.subject | fluorine | en |
dc.subject | substitution reaction | en |
dc.subject | Aromatic compounds | en |
dc.subject | 1,3 butadiene | en |
dc.subject | 2 phenylene chlorocarbenocarbene derivative | en |
dc.subject | 2 phenylene halocarbenonitrene derivative | en |
dc.subject | alkyne derivative | en |
dc.subject | benzochlorocyclobutadiene | en |
dc.subject | bromine | en |
dc.subject | Butadiene | en |
dc.subject | carbenoid | en |
dc.subject | Carbon inorganic compounds | en |
dc.subject | Halogen compounds | en |
dc.subject | Matrix isolation | en |
dc.subject | O-phenylene chlorocarbenocarbene | en |
dc.subject | O-phenylene halocarbenonitrene | en |
dc.subject | photoreactivity | en |
dc.subject | ring closing metathesis | en |
dc.subject | ring opening | en |
dc.subject | Ring opening polymerization | en |
dc.subject | Ring-opening reactions | en |
dc.title | o-Phenylene halocarbenonitrenes and o-phenylene chlorocarbenocarbene: A combined experimental and computational approach | en |
dc.type | info:eu-repo/semantics/article | |
dc.identifier.doi | 10.1021/jo0512204 | |
dc.description.volume | 70 | |
dc.description.issue | 19 | |
dc.description.startingpage | 7744 | |
dc.description.endingpage | 7754 | |
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 :9</p> | en |
dc.source.abbreviation | J.Org.Chem. | en |
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