Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance work on Wednesday 21st October 2020 from 07:00 AM to 07:00 PM (BST).

During this time our website performance may be temporarily affected. We apologise for any inconvenience this might cause and thank you for your patience.

Issue 4, 2001
Previous Article Next Article

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

Author affiliations


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 antisyn 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.

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

Back to tab navigation

Supplementary files

Article information

01 Nov 2000
24 Jan 2001
First published
16 Feb 2001

J. Chem. Soc., Perkin Trans. 2, 2001, 459-467
Article type

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

W. Cross, G. E. Hawkes, R. T. Kroemer, K. R. Liedl, T. Loerting, R. Nasser, R. G. Pritchard, M. Steele, M. Watkinson and A. Whiting, J. Chem. Soc., Perkin Trans. 2, 2001, 459
DOI: 10.1039/B008788M

Search articles by author