On the Mechanism of the Reactivity of 1,3-Dialkylimidazolium Salts under Basic to Acidic Conditions : A Combined Kinetic and Computational Study

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Rico del Cerro , D , Mera-Adasme , R , King , A W T , Perea-Buceta , J E , Heikkinen , S , Hase , T , Sundholm , D & Wähälä , K 2018 , ' On the Mechanism of the Reactivity of 1,3-Dialkylimidazolium Salts under Basic to Acidic Conditions : A Combined Kinetic and Computational Study ' , Angewandte Chemie (International Edition) , vol. 57 , no. 36 , pp. 11613-11617 . https://doi.org/10.1002/anie.201805016

Title: On the Mechanism of the Reactivity of 1,3-Dialkylimidazolium Salts under Basic to Acidic Conditions : A Combined Kinetic and Computational Study
Author: Rico del Cerro, Daniel; Mera-Adasme, Raúl; King, Alistair W. T.; Perea-Buceta, Jesus E.; Heikkinen, Sami; Hase, Tapio; Sundholm, Dage; Wähälä, Kristiina
Contributor: University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
University of Helsinki, Laboratory for Instruction in Swedish (-2016)
University of Helsinki, Medicum
Date: 2018-09-03
Language: eng
Number of pages: 5
Belongs to series: Angewandte Chemie (International Edition)
ISSN: 1433-7851
URI: http://hdl.handle.net/10138/307509
Abstract: Comprehensive spectroscopic kinetic studies illustrate an alternative mechanism for the traditional free-carbene intermediated H/D exchange reaction of 1,3-dialkylimidazolium salts under neutral (D2O) and acidic conditions (DCl/D2O 35wt% solution). The deuteration of high purity [bmim]Cl in D2O is studied at different temperatures, in absence of catalyst or impurities, to yield an activation energy. DFT transition-state modelling, of a small water cluster and [bmim] cation, also yields an activation energy which strongly supports the proposed mechanism. The presence of basic impurities are shown to significantly enhance the exchange reaction, which brings into question the need for further analysis of technical purities of ionic liquids and the implications for a wide range of chemical reactions in such media.
Subject: 116 Chemical sciences
carbenes
hydrogen bonds
ionic liquids
kinetics
transition states
N-HETEROCYCLIC CARBENES
ACETATE IONIC LIQUIDS
BASIS-SETS
UNWANTED ACETYLATION
HYDROGEN-BONDS
H/D EXCHANGE
CELLULOSE
POLYSACCHARIDES
CHEMISTRY
CATALYSIS
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