Ionic Liquids and Dense Carbon Dioxide: A Beneficial Biphasic System for Catalysis

Jutz, Fabian; Andanson, Jean‐Michel; Baiker, Alfons

doi:10.1021/cr100194q

Cited by 287 publications

(209 citation statements)

References 235 publications

(524 reference statements)

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“…[1][2][3][4][5][6][7][8][9][10][11] In this context, imidazolium acetate based ILs were proposed as systems able to capture comparatively to other ionic liquids, unusual amounts of carbon dioxide. 12,13 A number of investigations by us and others have shown that carbon dioxide dissolved in dried 1-butyl-3-methylimidazolium acetate [Bmim] [Ac] a) Author to whom correspondence should be addressed.…”

Section: Introductionmentioning

confidence: 99%

Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

Cabaço¹,

Besnard

Chávez

et al. 2014

The Journal of Chemical Physics

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NMR spectroscopy ( 1 H, 13 C, 15 N) shows that carbon disulfide reacts spontaneously with 1-butyl-1-methylpyrrolidinium acetate ([BmPyrro][Ac]) in the liquid phase. It is found that the acetate anions play an important role in conditioning chemical reactions with CS 2 leading, via coupled complex reactions, to the degradation of this molecule to form thioacetate anion (CH 3 COS − ), CO 2 , OCS, and trithiocarbonate (CS 3 2− ). In marked contrast, the cation does not lead to the formation of any adducts allowing to conclude that, at most, its role consists in assisting indirectly these reactions. The choice of the [BmPyrro] + cation in the present study allows disentangling the role of the anion and the cation in the reactions. As a consequence, the ensemble of results already reported on (2), and CO 2 - [Bmim][Ac] (3) systems can be consistently rationalized. It is argued that in system (1) both anion and cation play a role. The CS 2 reacts with the acetate anion leading to the formation of CH 3 COS − , CO 2 , and OCS. After these reactions have proceeded the nascent CO 2 and OCS interact with the cation to form imidazolium-carboxylate ([Bmim] CO 2 ) and imidazoliumthiocarboxylate ([Bmim] COS). The same scenario also applies to system (2). In contrast, in the CO 2 - [Bmim] [Ac] system a concerted cooperative process between the cation, the anion, and the CO 2 molecule takes place. A carbene issued from the cation reacts to form the [Bmim] CO 2 , whereas the proton released by the ring interacts with the anion to produce acetic acid. In all these systems, the formation of adduct resulting from the reaction between the solute molecule and the carbene species originating from the cation is expected. However, this species was only observed in systems (2) and (3). The absence of such an adduct in system (1) has been theoretically investigated using DFT calculations. The values of the energetic barrier of the reactions show that the formation of [Bmim] CS 2 is unfavoured and that the anion offers a competitive reactive channel via an oxygensulphur exchange mechanism with the solute in systems (1) and (2). © 2014 AIP Publishing LLC.

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Section: Introductionmentioning

confidence: 99%

Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

Cabaço¹,

Besnard

Chávez

et al. 2014

The Journal of Chemical Physics

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“…[18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] The study of the interaction of carbon dioxide with molecular liquids and complex fluids as ionic liquids is a field of current interest, motivated not only from the fundamental point of view but mainly under the impetuous motivation of understanding the interactions of CO 2 in the field of environmental studies. [67][68][69][70] Surprisingly, in this context, studies of the CO 2 -CS 2 binary mixture are extremely scarce. In gaseous phase, a single spectroscopic study using infrared laser to probe the asymmetric stretch of CO 2 in a CO 2 -CS 2 a) Author to whom correspondence should be addressed.…”

Section: Introductionmentioning

confidence: 99%

Assessing the non-ideality of the CO2-CS2 system at molecular level: A Raman scattering study

Besnard

Cabaço²,

Coutinho

et al. 2013

The Journal of Chemical Physics

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The dense phase of CO 2 -CS 2 mixtures has been analysed by Raman spectroscopy as a function of the CO 2 concentration (0.02-0.95 mole fractions) by varying the pressure (0.5 MPa up to 7.7 MPa) at constant temperature (313 K). The polarised and depolarised spectra of the induced (ν 2 , ν 3 ) modes of CS 2 and of the ν 1 -2ν 2 Fermi resonance dyad of both CO 2 and CS 2 have been measured. Upon dilution with CO 2 , the evolution of the spectroscopic observables of all these modes displays a "plateau-like" region in the CO 2 mole fraction 0.3-0.7 never previously observed in CO 2 -organic liquids mixtures. The bandshape and intensity of the induced modes of CS 2 are similar to those of pure CS 2 up to equimolar concentration, after which variations occur. The preservation of the local ordering from pure CS 2 to equimolar concentration together with the non-linear evolution of the spectroscopic observables allows inferring that two solvation regimes exist with a transition occurring in the plateau domain. In the first regime, corresponding to CS 2 concentrated mixtures, the liquid phase is segregated with dominant CS 2 clusters, whereas, in the second one, CO 2 monomers and dimers and CO 2 -CS 2 hetero-dimers coexist dynamically on a picosecond time-scale. It is demonstrated that the subtle interplay between attractive and repulsive interactions which provides a molecular interpretation of the non-ideality of the CO 2 -CS 2 mixture allows rationalizing the volume expansion and the existence of the plateau-like region observed in the pressure-composition diagram previously ascribed to the proximity of an upper critical solution temperature at lower temperatures.

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“…Ionic liquids (ILs), made of relatively large organic cations and inorganic anions, could contribute as solvents and catalysts to green organic synthetic reactions [1][2][3][4][5]. The reaction systems using no organic solvents, dense phase carbon dioxide (supercritical and carbon dioxide-dissolved expanded liquid phases), and/or water are obviously advantageous from environmental viewpoints [1].…”

Section: Introductionmentioning

confidence: 99%

“…1. It is evidenced that ILs act as good catalysts for several organic synthetic reactions, as noted in recent review articles [1][2][3][4][5], including Friedel-Crafts reactions, Diels-Alder reactions, hydrogenation, polymerization, and other reactions. Haumann and Riisager discuss various aspects (structure of substrates, type of ILs, form of ILs catalysts) in hydroformylation reactions using ILs [4].…”

Section: Introductionmentioning

confidence: 99%

“…Haumann and Riisager discuss various aspects (structure of substrates, type of ILs, form of ILs catalysts) in hydroformylation reactions using ILs [4]. Recently Baiker et al have published a review on multiphase catalytic systems including ILs and carbon dioxide [5]. They point out the significance of the combination of ILs and carbon dioxide for chemical and separation processes.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Ionic Liquids in Green Carbonate Synthesis

Sun¹,

Liu²,

Fujita³

et al. 2011

Ionic Liquids - Classes and Properties

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Ionic Liquids and Dense Carbon Dioxide: A Beneficial Biphasic System for Catalysis

Cited by 287 publications

References 235 publications

Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

Assessing the non-ideality of the CO2-CS2 system at molecular level: A Raman scattering study

Ionic Liquids in Green Carbonate Synthesis

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