title: Carbene formation in ionic liquids: spontaneous, induced, or prohibited?
abstract: We present a theoretical study of carbene formation from the 1-ethyl-3-methylimidazolium acetate ionic liquid in the absence and presence of CO2 in gas and liquid phase. Although CO2 physisorption constitutes a precursory step of chemisorption (the CO2's reaction with carbenes, which forms from cations via proton abstraction by anions), it also enables a very stable CO2-anion associate. However, this counteracts the chemical absorption by reducing the basicity of the anion and the electrophilicity of the CO2, which is reflected by charge transfer. Accordingly, the observable carbene formation in the gas phase is hindered in the presence of CO2. In the neat liquid, the carbene formation is also suppressed by the charge screening compared to the case of the gas phase; nevertheless, indications for carbene incidents appear. Interestingly, in the CO2-containing liquid we detect more carbene-like incidents than in the neat one, which is caused by the way CO2 is solvated. Despite the weakness of the CO2-cation interaction, the CO2-anion associate is distorted by cations, which can be seen in longer associate distances and reduced "binding" energies. While the single solvating anion is shifted away from CO2, many more solvating cations approach it compared to the case of the gas phase. This leads to the conclusion that while the ionic liquid effect stabilizes charged species, introducing neutral species such as CO2 provides an opposite trend, leading to an inverse ionic liquid effect with the facilitation of carbene formation and thus of chemical absorption.
authors.affiliation: Mulliken Centre for Theoretical Chemistry, University of Bonn, Beringstraße 4, D-53115 Bonn, Germany. holloczki@gmail.com
authors.forename: Oldamur
authors.initials: O
authors.lastname: Hollóczki
authors.forename: Dzmitry S
authors.initials: DS
authors.lastname: Firaha
authors.forename: Joachim
authors.initials: J
authors.lastname: Friedrich
authors.forename: Martin
authors.initials: M
authors.lastname: Brehm
authors.forename: Richard
authors.initials: R
authors.lastname: Cybik
authors.forename: Martin
authors.initials: M
authors.lastname: Wild
authors.forename: Annegret
authors.initials: A
authors.lastname: Stark
authors.forename: Barbara
authors.initials: B
authors.lastname: Kirchner