The structure, modelling and dynamics of hindered 5, 6-diarylacenaphthenes

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dc.contributor.author Nasser, Rima
dc.contributor.author Cross, Wendy
dc.contributor.author Hawkes, Geoffrey E.
dc.contributor.author Kroemer, Romano T.
dc.contributor.author Liedl, Klaus
dc.date.accessioned 2019-04-09T08:51:49Z
dc.date.available 2019-04-09T08:51:49Z
dc.date.copyright 2001 en_US
dc.identifier.issn 1364-5471 en_US
dc.identifier.uri http://hdl.handle.net/10725/10378
dc.description.abstract A series of 5,6-diarylacenaphthenes, 2–4, has been investigated using a variety of theoretical and experimental methods. The purpose of the investigation was to gain a thorough understanding of the dynamics of atropisomer interconversion in these molecules. Quantum chemical calculations were performed at different levels, including Hartree–Fock theory, density functional theory (B3LYP), and a semi-empirical method (AM1). Basis sets used ranged from STO-3G to 6-31+G*. The structures of energy minima and transition states for anti–syn interconversion were fully optimised. A geometrical comparison of the single-crystal X-ray structures of syn-2b, anti-2c and anti-2d was made with the results from the calculations, and revealed excellent agreement in most cases. Theoretical barriers to rotation were compared with those derived experimentally by NMR spectroscopy. Again excellent correlation between theoretical and experimental values was found. In the transition states a significant deviation from planarity for the acenaphthene moiety was calculated. The transition state structures indicate why bulky substituents, such as But, in the 3′ and 3″ positions of the peri-aryl rings are not able to prevent atropisomer interconversion. The structures provide a good explanation for the trends observed in experimental barriers to rotation. en_US
dc.language.iso en en_US
dc.title The structure, modelling and dynamics of hindered 5, 6-diarylacenaphthenes en_US
dc.type Article en_US
dc.description.version Published en_US
dc.author.school SOM en_US
dc.author.idnumber 200904844 en_US
dc.author.department N/A en_US
dc.description.embargo N/A en_US
dc.relation.journal Journal of the Chemical Society, Perkin Transactions 2 en_US
dc.journal.issue 4 en_US
dc.article.pages 459-467 en_US
dc.identifier.ctation Cross, W., Hawkes, G. E., Kroemer, R. T., Liedl, K. R., Loerting, T., Nasser, R., ... & Whiting, A. (2001). The structure, modelling and dynamics of hindered 5, 6-diarylacenaphthenes. Journal of the Chemical Society, Perkin Transactions 2, (4), 459-467. en_US
dc.author.email rima.nasser@lau.edu.lb en_US
dc.identifier.tou http://libraries.lau.edu.lb/research/laur/terms-of-use/articles.php en_US
dc.identifier.url https://pubs.rsc.org/en/content/articlelanding/2001/p2/b008788m/unauth#!divAbstract en_US
dc.author.affiliation Lebanese American University en_US

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