Manipulating Solute Nucleophilicity with Room Temperature Ionic Liquids

Crowhurst, Lorna; Lancaster, N. Llewellyn; Arlandis, Juan M. Perez; Welton, Tom

doi:10.1021/ja046757y

Cited by 243 publications

(202 citation statements)

References 40 publications

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“…Indeed, according to previous reports, 19 among aromatic protons of imidazolium ion, the H2 proton is the one able to give the strongest interaction with the anion and, consequently, it is the most affected by amine presence. A similar amine structure effect was previously found by Welton et al 20 and subsequently confirmed by us. 21 On the other hand, this interaction allows us to rationalize the lowest influence of the amine presence on the aliphatic protons of imidazolium ion, not interacting, with the IL anion.…”

Section: Issn 1551-7012supporting

confidence: 91%

The effect of some amines and alcohols on the organized structure of [bmim][BF4] investigated by 1H NMR spectroscopy

Cascino¹,

Meo²,

Riela³

et al. 2008

Arkivoc

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The effect exerted by some amines and alcohols on the 1 H NMR spectra of 1-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF4] has been studied. This ionic liquid, which is one of the most widely used, is characterized by a high structural order degree, as a consequence of the symmetry and the coordination ability of the anion. In order to have information about the dependence of the detected effects on the alcohol or amine structure, some different primary, secondary and tertiary amines and alcohols have been considered. Furthermore, in the case of amines, their basicity has been also taken into account. Both amines and alcohols induce variation in chemical shifts values and signal multiplicity of imidazolium protons. Collected data show that, among imidazolium protons, the aromatic ones are the most affected by the presence of organic molecule. Cross-correlations among chemical shift values relevant to these protons allow us to explain how 1 H NMR spectrum variations depend on probe structural properties.

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Section: Issn 1551-7012supporting

confidence: 91%

The effect of some amines and alcohols on the organized structure of [bmim][BF4] investigated by 1H NMR spectroscopy

Cascino¹,

Meo²,

Riela³

et al. 2008

Arkivoc

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“…A high yield of an organic reaction can be obtained by the choice of a suitable ionic liquid or a binary mixture of two or more ionic liquids, see e.g., Refs. [29][30][31]. RTILs have been used as solvent media for organic synthesis and new types of catalysts, lubricants, carbon-nano tubes, etc.…”

Section: N]mentioning

confidence: 99%

Raman Spectroscopy and Ab-Initio Model Calculations on Ionic Liquids

2007

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Summary.A review of the recent developments in the study and understanding of room temperature ionic liquids are given. An intimate picture of how and why these liquids are not crystals at ambient conditions is attempted, based on evidence from crystallographical results combined with vibrational spectroscopy and ab-initio molecular orbital calculations. A discussion is given, based mainly on some recent FT-Raman spectroscopic results on the model ionic liquid system of 1-butyl-3-methylimidazolium ([C 4 mim][X]) salts. The rotational isomerism of the [C 4 mim] þ cation is described: the presence of anti and gauche conformers that has been elucidated in remarkable papers by Hamaguchi et al. Such presence of a conformational equilibrium seems to be a general feature of the room temperature liquids. Then the ''localized structure features'' that apparently exist in ionic liquids are described. It is hoped that the structural resolving power of Raman spectroscopy will be appreciated by the reader. It is of remarkable use on crystals of known different conformations and on the corresponding liquids, especially in combination with modern quantum mechanics calculations. It is hoped that these interdisciplinary methods will be applied to many more systems in the future. A few examples will be discussed.

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“…The intense scientific interest in RTILs stems from their complex combination of interactions, van der Waals, Coulomb, dipole, and hydrogen bonding, rarely occurring simultaneously in other materials [5,6]. Being infiniteconcentration ionic "solutions", RTILs are strongly correlated systems, going beyond the validity regime of the Poisson-Boltzman equation, and the Gouy-Chapman and Stern models of the electric double layer [7], and thus allowing insight into this scarcely studied regime.…”

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confidence: 99%