We report the first example of an alkene with two carbon-bound substituents (imidazole and imidazolium rings) where the Z-isomer has a greater thermodynamic stability than the E-isomer which persists in both the gas phase and in solution. Theoretical calculations, solution fluorescence spectroscopy and gas-phase ion mobility mass spectrometry studies confirm the preference for the Z-isomer, the stability of which is traced to a non-covalent interaction between the imidazole lone pair and the imidazolium ring.
Funding
We thank the La Trobe Institute for Molecular Sciences, Melbourne University and the Australian Research Council (JLD, DE130100186, FT160100007; EJB DP150101427 and DP160100474) for their generous funding of this project. We acknowledge generous allocations of computing from La Trobe University, Intersect, and NCI.
Publication Date
2017-01-01Journal
Angewandte Chemie International EditionVolume
56Issue
29Pagination
8p. (p. 8473-8480)Publisher
John Wiley & Sons Ltd.ISSN
1433-7851Rights Statement
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. This is the peer reviewed version of the following article: Georgiou DC, et al (2017). A strong cis-effect in an imidazole-imidazolium-substituted alkene. Angewandte Chemie - International Edition, 56(29), 8473-8480, which has been published in final form at http://doi.org/10.1002/anie.201702287. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.
