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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| Authors: | M?Sc Daniel Rico?del?Cerro Prof Raúl Mera‐Adasme Dr Alistair W T King Dr Jesus E Perea‐Buceta Dr Sami Heikkinen Prof Tapio Hase Prof Dage Sundholm Prof Kristiina Wähälä |
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| Institution: | 1. Department of Chemistry, University of Helsinki, Helsinki, Finland;2. Departamento de Ciencias del Ambiente, Facultad de Química y Biología, Universidad de Santiago de Chile, Estacion Central, Chile;3. Department of Biochemistry and Development Biology, University of Helsinki, Helsinki, Finland |
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| 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. |
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| Keywords: | carbenes hydrogen bonds ionic liquids kinetics transition states |
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