On the mechanism of the reactivity of 1,3-dialkylimidazolium salts under basic to acidic conditions: a combined kinetic and computational study.

On the mechanism of the reactivity of 1,3-dialkylimidazolium salts under basic to acidic conditions: a combined kinetic and computational study.
Angew Chem Int Ed Engl. 2018 Jul 10;:
Authors: Rico Del Cerro D, Mera Adasme R, King AWT, Perea Buceta JE, Heikkinen S, Hase T, Sundholm D, Wähälä K
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 35 wt % 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.
PMID: 29987916 [PubMed - as supplied by publisher]

Source: Angewandte Chemie - July 10, 2018 Category: Chemistry Authors: Rico Del Cerro D, Mera Adasme R, King AWT, Perea Buceta JE, Heikkinen S, Hase T, Sundholm D, Wähälä K Tags: Angew Chem Int Ed Engl Source Type: research