Effect of Modifying the Anion of an Ionic Liquid on the Outcome of an SN2 Process

2015 ◽  
Vol 68 (1) ◽  
pp. 31 ◽  
Author(s):  
Sinead T. Keaveney ◽  
Dominic V. Francis ◽  
Winnie Cao ◽  
Ronald S. Haines ◽  
Jason B. Harper
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Rate Constant ◽  
Kinetic Data ◽  
Activation Parameters ◽  
Temperature Dependent ◽  
Substitution Process

The effect of a series of ionic liquids containing different anions (bis(trifluoromethanesulfonyl)imide, dicyanimide, hexafluorophosphate, tetrafluoroborate, and bromide) on the rate constant of a bimolecular substitution process was investigated. A general ionic liquid effect was noted, with increases in the rate constant observed in all ionic liquids used when compared with that in acetonitrile. Temperature-dependent kinetic data allowed calculation of activation parameters in each of the reaction mixtures considered; these parameters showed that the microscopic origins of the rate enhancements observed were not the same for all of the ionic liquids used, demonstrating the importance of the nature of the anion.

Understanding the effects of ionic liquids on a unimolecular substitution process: correlating solvent parameters with reaction outcome

2019 ◽  
Vol 17 (3) ◽  
pp. 675-682 ◽  
Author(s):  
Alyssa Gilbert ◽  
Ronald S. Haines ◽  
Jason B. Harper
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Rate Constant ◽  
Solvent Parameters ◽  
Substitution Process

The polarisability of an ionic liquid is key in determining the rate constant of a unimolecular substitution process.

Rational selection of the cation of an ionic liquid to control the reaction outcome of a substitution reaction

2018 ◽  
Vol 54 (18) ◽  
pp. 2296-2299 ◽  
Author(s):  
Rebecca R. Hawker ◽  
Ronald S. Haines ◽  
Jason B. Harper
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Rate Constant ◽  
Substitution Reaction ◽  
Rational Selection ◽  
Substitution Process ◽  
Selection Of

Rational selection of ionic liquids to get the rate constant you want in a substitution process.

Rapid relaxation NMR measurements to predict rate coefficients in ionic liquid mixtures. An examination of reaction outcome changes in a homologous series of ionic liquids

2021 ◽  
Author(s):  
Daniel C Morris ◽  
Stuart W Prescott ◽  
Jason B Harper
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Homologous Series ◽  
Rate Coefficient ◽  
Liquid Mixtures ◽  
Solvent Mixture ◽  
Rate Coefficients ◽  
Substitution Process

A series of ionic liquids based on the 1-alkyl-3-methylimidazolium cations were examined as components of the solvent mixture for a bimolecular substitution process. The effects on both the rate coefficient...

Controlling the reactions of 1-bromogalactose acetate in methanol using ionic liquids as co-solvents

2020 ◽  
Vol 18 (28) ◽  
pp. 5442-5452 ◽  
Author(s):  
Alyssa Gilbert ◽  
Ronald S. Haines ◽  
Jason B. Harper
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Rate Constant ◽  
Solvent Mixture ◽  
Solvent Composition ◽  
Composition Changes

Using an ionic liquid in the solvent mixture for the reaction of a galactose substrate leads to changes in both the rate constant and the products as the solvent composition changes.

scholarly journals Kinetics of solvolysis in water of four secondary alkyl nitrates

1982 ◽  
Vol 60 (13) ◽  
pp. 1780-1785 ◽  
Author(s):  
Ross Elmore Robertson ◽  
Kalvelil Matthew Koshy ◽  
Adrianne Annessa ◽  
Jan N. Ong ◽  
John Marshall William Scott ◽  
...  
Keyword(s):  
Heat Capacity ◽  
Rate Constant ◽  
Analytical Methods ◽  
Kinetic Data ◽  
Activation Parameters ◽  
Single Step ◽  
Alkyl Nitrates ◽  
Two Stage ◽  
Kinetics Of ◽  
Single Step Reaction

Kinetic data are reported for the solvolysis in water of propane-2-nitrate, butane-2-nitrate, cyclopentyl nitrate, and cyclohexyl nitrate. In each case, the dependence of rate constant on temperature is analysed in terms of two mechanisms for the solvolytic reaction. First it is assumed that the rate constant describes a single step reaction, the analysis leading to estimates of the heat capacity of activation ΔCp≠. Three different analytical methods are discussed in this regard. Second it is assumed that the rate constant describes a two stage mechanism, the first stage being reversible. In this case the explanation of the ΔCp≠ term calculated according to the first mechanism is quite different. We comment on the alternative explanations of trends in activation parameters.

Correlating ionic liquid solvent effects with solvent parameters for a reaction that proceeds through a xanthylium intermediate

2019 ◽  
Vol 17 (42) ◽  
pp. 9336-9342 ◽  
Author(s):  
Alyssa Gilbert ◽  
Götz Bucher ◽  
Ronald S. Haines ◽  
Jason B. Harper
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Rate Constant ◽  
Solvent Effects ◽  
Solvent Parameters

The effects of ionic liquids on the rate constant of an SN1 process with a xanthylium intermediate differ from those observed for other SN1 reactions. These effects can be correlated to solvent parameters of the ionic liquids allowing predictability.

scholarly journals Thermochromism and switchable paramagnetism of cobalt(ii) in thiocyanate ionic liquids

2015 ◽  
Vol 44 (25) ◽  
pp. 11286-11289 ◽  
Author(s):  
Stephen J. Osborne ◽  
Sil Wellens ◽  
Chris Ward ◽  
Solveig Felton ◽  
Robert M. Bowman ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Liquid Solution ◽  
Temperature Dependent ◽  
Ionic Liquid Solution

Temperature-dependent switching of paramagnetism of a cobalt(ii) complex is observed in an ionic liquid solution.

Temperature-Dependent Solvatochromic Probe Behavior within Ionic Liquids and (Ionic Liquid + Water) Mixtures

2010 ◽  
Vol 114 (24) ◽  
pp. 8118-8125 ◽  
Author(s):  
Shruti Trivedi ◽  
Naved I. Malek ◽  
Kamalakanta Behera ◽  
Siddharth Pandey
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Liquid Water ◽  
Temperature Dependent

scholarly journals Developing principles for predicting ionic liquid effects on reaction outcome. The importance of the anion in controlling microscopic interactions

2015 ◽  
Vol 13 (12) ◽  
pp. 3771-3780 ◽  
Author(s):  
Sinead T. Keaveney ◽  
Ronald S. Haines ◽  
Jason B. Harper
Keyword(s):  
Ionic Liquid ◽  
Rate Constant ◽  
Condensation Reaction ◽  
Activation Parameters ◽  
Solvent Composition ◽  
Microscopic Interactions

Predictable changes in the rate constant of a condensation reaction were seen as the solvent composition was varied. The cation–nucleophile interaction could be controlled in a predictable manner; activation parameters varied linearly with the H-bond acceptor ability of the anions used.

Mapping the “Extra Solvent Power, ESP” of Ionic Liquids for Monomers, Polymers and Globular Nanoparticles

2017 ◽  
Author(s):  
Jose A. Pomposo
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Linear Polymers ◽  
Green Solvents ◽  
Ionic Polymers ◽  
First Time ◽  
Solvent Power

Understanding the miscibility behavior of ionic liquid (IL) / monomer, IL / polymer and IL / nanoparticle mixtures is critical for the use of ILs as green solvents in polymerization processes, and to rationalize recent observations concerning the superior solubility of some proteins in ILs when compared to standard solvents. In this work, the most relevant results obtained in terms of a three-component Flory-Huggins theory concerning the “Extra Solvent Power, ESP” of ILs when compared to traditional non-ionic solvents for monomeric solutes (case I), linear polymers (case II) and globular nanoparticles (case III) are presented. Moreover, useful ESP maps are drawn for the first time for IL mixtures corresponding to case I, II and III. Finally, a potential pathway to improve the miscibility of non-ionic polymers in ILs is also proposed.

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