Next Article in Journal
Preparation, Characterization and Efficacy Evaluation of Synthetic Biocompatible Polymers Linking Natural Antioxidants
Next Article in Special Issue
Radioiodination of Aryl-Alkyl Cyclic Sulfates
Previous Article in Journal
An Efficient Synthesis of Novel Dispirooxindole Derivatives via One-Pot Three-Component 1,3-Dipolar Cycloaddition Reactions
Previous Article in Special Issue
Synthesis of Highly Substituted Oxazoles through Iodine(III)-Mediated Reactions of Ketones with Nitriles
Article Menu

Export Article

Open AccessArticle
Molecules 2012, 17(11), 12718-12733;

17O-Dynamic NMR and DFT Investigation of Bis(acyloxy)iodoarenes

Laboratoire de RMN Haute Résolution CP 160/08, Université Libre de Bruxelles, Av. F.-D. Roosevelt 50, 1050 Brussels, Belgium
Dipartimento di Scienze Chimiche e Geologiche, Università di Cagliari, Complesso Universitario, S.S. 554, Bivio per Sestu, I-09042 Monserrato (CA), Italy
Authors to whom correspondence should be addressed.
Received: 11 September 2012 / Revised: 10 October 2012 / Accepted: 19 October 2012 / Published: 26 October 2012
(This article belongs to the Special Issue Organic Iodine Chemistry 2012)
Full-Text   |   PDF [754 KB, uploaded 18 June 2014]   |  


Bis(acetoxy)iodobenzene and related acyloxy derivatives of hypervalent I(III) were studied by variable temperature solution-state 17O-NMR and DFT calculations. The 17O-NMR spectra reveal a dynamic process that interchanges the oxygen atoms of the acyloxy groups. For the first time, coalescence events could be detected for such compounds, allowing the determination of activation free energy data which are found to range between 44 and 47 kJ/mol. The analysis of the 17O linewidth measured for bis(acetoxy)iodobenzene indicates that the activation entropy is negligible. DFT calculations show that the oxygen atom exchange arises as a consequence of the [1,3]-sigmatropic shift of iodine. The calculated activation barriers are in excellent agreement with the experimental results. Both the 17O-NMR and DFT studies show that the solvent and chemical alterations, such as modification of the acyl groups or para- substitution of the benzene ring, hardly affect the energetics of the dynamic process. The low I-O Wiberg bond index (0.41–0.42) indicates a possible explanation of the invariance of both the energy barrier and the 17O chemical shift with para-substitution. View Full-Text
Keywords: hypervalent iodine; fluxional compounds; sigmatropic shift; 17O-NMR; chemical exchange; Density Functional Theory hypervalent iodine; fluxional compounds; sigmatropic shift; 17O-NMR; chemical exchange; Density Functional Theory

Graphical abstract

This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

Supplementary material


Share & Cite This Article

MDPI and ACS Style

Fusaro, L.; Mocci, F.; Luhmer, M.; Cerioni, G. 17O-Dynamic NMR and DFT Investigation of Bis(acyloxy)iodoarenes. Molecules 2012, 17, 12718-12733.

Show more citation formats Show less citations formats

Related Articles

Article Metrics

Article Access Statistics



[Return to top]
Molecules EISSN 1420-3049 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top