Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 20, Issue 40, Pages 13002-13008Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201402912
Keywords
basicity; density functional calculations; ionic liquids; N-heterocyclic carbenes; supercritical CO2
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Funding
- OTKA [K 105417]
- COST [CM1206 EXIL]
- Alexander von Humboldt Foundation
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In the reaction of 1-ethyl-3-methylimidazolium acetate [C(2)C(1)Im][0Ac] ionic liquid with carbon dioxide at 125 C and 10 MPa, not only the known N-heterocyclic carbene (NHC) CO2 adduct I, but also isomeric aNHC-CO2 adducts II and III were obtained. The abnormal NHC-CO2 adducts are stabilized by the presence of the polarizing basic acetate anion, according to static DFT calculations and ab initio molecular dynamics studies. A further possible reaction pathway is facilitated by the high basicity of the system, deprotonating the initially formed NHC-CO2 adduct I, which can then be converted in the presence of the excess of CO2 to the more stable 2-deprotonated anionic abnormal NHC CO2 adduct via the anionic imidazolium-2,4-dicarboxylate according to DFT calculations on model compounds. This suggests a generalizable pathway to abnormal NHC complex formation.
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