Undoing lithium ion association in ionic liquids through the complexation by oligoethers

Tetraglyme (TG) and the recently developed trimethylsilyl capped analogue (1NM3) when used as additives in a N-methyl-N-propylpyrrolidinium bis(trifluoromethylsulfonyl) amide [C₃mpyr][NTf₂]/0.65 M LiNTf₂ electrolyte have been shown to dramatically enhance the transport properties of this electrolyte. In fact, at a concentration of 20 mol % tetraglyme (leading to a ratio of ~1:1 ether molecule per lithium ion), viscosity, conductivity, and the diffusion coefficients of the C₃mpyr⁺ and NTf₂⁻ are practically reinstated to the values observed in the absence of lithium, thereby negating the structuring effects of the lithium ion. The ⁷Li T₁ relaxation times also indicate that these additives strongly interact with the lithium ions. Furthermore, although TG has twice the viscosity of 1NM3, the greatest improvement in transport properties was observed for TG.

Extraction of copper(II) ions from aqueous solutions with a methimazole-based ionic liquid

The recently synthesized ionic liquid (IL) 2-butylthiolonium bis(trifluoromethanesulfonyl)amide, [mimSBu][NTf2], has been used for the extraction of copper(II) from aqueous solution. The pH of the aqueous phase decreases upon addition of [mimSBu]+, which is attributed to partial release of the hydrogen attached to the N(3) nitrogen atom of the imidazolium ring. The presence of sparingly soluble water in [mimSBu][NTf2] also is required in solvent extraction studies to promote the incorporation of Cu(II) into the [mimSBu][NTf2] ionic liquid phase. The labile copper(II) system formed by interacting with both the water and the IL cation component has been characterized by cyclic voltammetry as well as UV−vis, Raman, and 1H, 13C, and 15N NMR spectroscopies. The extraction process does not require the addition of a complexing agent or pH control of the aqueous phase. [mimSBu][NTf2] can be recovered from the labile copper−water−IL interacting system by washing with a strong acid. High selectivity of copper(II) extraction is achieved relative to that of other divalent cobalt(II), iron(II), and nickel(II) transition-metal cations. The course of microextraction of Cu2+ from aqueous media into the [mimSBu][NTf2] IL phase was monitored in situ by cyclic voltammetry using a well-defined process in which specific interaction with copper is believed to switch from the ionic liquid cation component, [mimSBu], to the [NTf2] anion during the course of electrochemical reduction from Cu(II) to Cu(I). The microextraction−voltammetry technique provides a fast and convenient method to determine whether an IL is able to extract electroactive metal ions from an aqueous solution.

Nonadditivity of faradaic currents and modification of double layer capacitance in the voltammetry of mixtures of ferrocene and ferrocenium salts in ionic liquids

Electrochemical studies on the Fc + e− Fc+ (Fc = ferrocene) process have been undertaken via the oxidation of Fc and reduction of Fc+ as the hexafluorophosphate (PF6−) or tetrafluoroborate (BF4−) salts and their mixtures in three ionic liquids (ILs) (1-butyl-1-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide, 1-butyl-3-methylimidazolium tetrafluoroborate, and 1-butyl-3-methylimidazolium hexafluorophosphate). Data obtained at macro- and microdisk electrodes using conventional dc and Fourier-transformed large-amplitude ac (FT-ac) voltammetry reveal that diffusion coefficients for Fc and Fc+ differ significantly and are a function of the Fc and Fc+ concentration, in contrast to findings in molecular solvents with 0.1 M added supporting electrolyte media. Thus, the Faradaic currents associated with the oxidation of Fc (Fc0/+) and reduction of FcPF6 or FcBF4 (Fc+/0) when both Fc and Fc+ are simultaneously present in the ILs differ from values obtained when individual Fc and Fc+ solutions are used. The voltammetry for both the Fc0/+ and Fc+/0 processes exhibited near-Nernstian behavior at a glassy carbon macrodisk electrode and a platinum microdisk electrode, when each process was studied individually in the ILs. As expected, the reversible formal potentials (E°′) and diffusion coefficients (D) at 23 ± 1 °C were independent of the electrode material and concentration. However, when Fc and FcPF6 or FcBF4 were both present, alterations to the mass transport process occurred and apparent D values calculated for Fc and Fc+ were found to be about 25−39% and 32−42% larger, respectively, than those determined from individual solutions. The apparent value of the double layer capacitance determined by FT-ac voltammetry from individual and mixed Fc and Fc+ conditions at the GC electrode was also a function of concentration. Double layer capacitance values increased significantly with the concentration of Fc and FcPF6 or FcBF4 when species were studied individually or simultaneously, but had a larger magnitude under conditions where both species were present. Variation in the structure of the ILs and hence mobilities of the ionic species, when Fc and FcPF6 or FcBF4 are simultaneously present, is considered to be the origin of the nonadditivity of the Faradaic currents and variation in capacitance.

Nonadditivity of Faradaic currents and modification of capacitance currents in the voltammetry of mixtures of ferrocene and the cobaltocenium cation in protic and aprotic ionic liquids

Unexpected nonadditivity of currents encountered in the electrochemistry of mixtures of ferrocene (Fc) and cobaltocenium cation (Cc+) as the PF6 - salt has been investigated by direct current (dc) and Fourier-transformed alternating current (ac) cyclic voltammetry in two aprotic (1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium hexafluorophosphate) and three protic (triethylammonium formate, bis(2-hydroxyethyl)ammonium acetate, and triethylammonium acetate) ionic liquids (ILs). The voltammetry of the individual Fc0/+ and Cc+/0 couples always exhibits near-Nernstian behavior at glassy carbon and gold electrodes. As expected for an ideal process, the reversible formal potentials and diffusion coefficients at 23 ( 1 °C in each IL determined from measurement on individual Fc and Cc+ solutions were found to be independent of electrode material, concentration, and technique used for the measurement. However, when Fc and Cc+ were simultaneously present, the dc and ac peak currents per unit concentration for the Fc0/+ and Cc+/0 processes were found to be significantly enhanced in both aprotic and protic ILs. Thus, the apparent diffusion coefficient values calculated for Fc and Cc+ were respectively found to be about 25 and 35% larger than those determined individually in the aprotic ILs. A similar change in the Fc0/+ mass transport characteristics was observed upon addition of tetrabutylammonium hexafluorophosphate (Bu4NPF6), and the double layer capacitance also varied in distinctly different ways when Fc and Cc+ were present individually or in mixtures. Importantly, the nonadditivity of Faradaic current is not associated with a change in viscosity or from electron exchange as found when some solutes are added to ILs. The observation that the 1H NMR T1 relaxation times for the proton resonance in Cc+ also are modified in mixed systems implies that specific interaction with aggregates of the constituent IL ionic species giving rise to subtle structural changes plays an important role in modifying the mass transport, double layer characteristics, and dynamics when solutes of interest in this study are added to ILs. Analogous voltammetric changes were not observed in studies in organic solvent media containing 0.1 M added supporting electrolyte. Implications of the nonadditivity of Faradaic and capacitance terms in ILs are considered.

Nitrile functionalized methimazole-based ionic liquids

The alkylation reaction of 2-mercapto-1-methylimidazole 1b with 2-chloroacetonitrile and 2-chloropropionitrile produced S-alkyl methimazole chlorides 2a and 2b which were subjected to anion metathesis with lithium bis(trifluoromethanesulfonyl)amide, LiNTf2, to afford nitrile functionalized methimazole-based room temperature ionic liquids 3a and 3b in 94% and 89% yields, respectively. Ionic liquids 3a and 3b have reasonably wide electrochemical windows. The efficient extraction of Ag+ from aqueous media into 3a and 3b is also reported.

Electrooxidation of [(η5-C5H5)Fe(CO)2]2 as a probe of the nucleophilic properties of ionic liquid anions

The oxidative electrochemistry of [CpFe(CO)2]2, 1 (Cp = [η5-C5H5]–), was examined in detail in ionic liquids (ILs) composed of ions of widely varying Lewis acid−base properties. Cyclic voltammetric responses were strongly dependent on the nucleophilic properties of the IL anion, but all observations are consistent with the initial formation of 1+ followed by attack from the IL anion. In [NTf2]–-based ILs ([NTf2]– = bis(trifluoromethylsulfonyl)amide), the process shows nearly ideal chemical reversibility as the reaction between 1+ and [NTf2]– is very slow. This is highly significant, as 1+ is known to be highly susceptible to nucleophilic attack and its stability indicates a remarkable lack of coordinating ability of these ILs. In 1-methyl-3-butylimidazolium hexafluorophosphate, [bmim][PF6], the oxidation of 1 is still largely reversible, but there is more pronounced evidence of [PF6]– coordination. In contrast, 1 exhibits an irreversible two-electron oxidation process in a dicyanamide-based IL. This overall oxidation process is thought to proceed via an ECE mechanism, details of which are presented. Rate constants were estimated by fitting the experimental data to digital simulations of the proposed mechanism. The use of [NTf2]–-based ILs as a supporting electrolyte in CH2Cl2 was examined by using this solvent/electrolyte as a medium in which to perform bulk electrolyses of 1 and 1*, the permethylated analogue [Cp*Fe(CO)2]2 (Cp* = [η5-C5(CH3)5]–). These cleanly yielded the corresponding binuclear radical-cation species, 1+ and 1*+, which were subsequently characterized by electron paramagnetic resonance (EPR) spectroscopy. In addition to the above oxidation studies, the reduction of 1 was studied in each of the ILs; differences in cathodic peak potentials are attributed, in part, to ion-pairing effects. This study illustrates the wide range of electrochemical environments available with ILs and demonstrates their utility for the investigation of the redox properties of metal carbonyls and other organometallic compounds.

Physical and electrochemical properties of thioether-functionalized ionic liquids

The preparation and characterization of a series of ionic liquids based on S-alkyl thiolonium, S-alkyl thiotetrazolium, or S-alkyl thiobenzolium cations coupled with bis(trifluoromethanesulfonyl)amide, trifluoromethanesulfonate, alkyl phosphate, chloride, and hexafluorophosphate anions are reported. All are liquid at room temperature, except the chloride salt, which has a melting point of 92 °C. The electrochemical characteristics of this class of ionic liquid have been determined by cyclic voltammetry. Potential windows of the ionic liquids have been obtained at glassy carbon, platinum, and gold electrodes and found to be the largest at glassy carbon, but are limited by oxidation of the thioether-functionalized cation. The voltammetry of IUPAC reference potential scale systems, ferrocene/ferrocenium, cobaltocenium/cobaltocene, and decamethylferrocene/decamethylferrocenium have been evaluated, with the last being most widely applicable. Nonadditivity of Faradaic current is found in the voltammograms of decamethylferrocene in the presence of ferrocene and cobaltocenium. Diffusion coefficient, viscosity, ionic conductivity, double layer capacitance, and other physical properties have also been measured. The dependence of the diffusion coefficient vs viscosity follows the Stokes−Einstein relationship. The properties of the ionic liquids are compared with the related imidazolium family of ionic liquids.

Electrochemistry of room temperature protic ionic liquids

Eighteen protic ionic liquids containing different combinations of cations and anions, hydrophobicity, viscosity, and conductivity have been synthesized and their physicochemical properties determined. In one series, the diethanolammonium cations were combined with acetate, formate, hydrogen sulfate, chloride, sulfamate, and mesylate anions. In the second series, acetate and formate anions were combined with amine bases, triethylamine, diethylamine, triethanolamine, di-n-propylamine, and di-n-butylamine. The electrochemical characteristics of the eight protic ionic liquids that are liquid at room temperature (RTPILs) have been determined using cyclic, microelectrode, and rotating disk electrode voltammetries. Potential windows of the RTPILs have been compared at glassy carbon, platinum, gold, and boron-doped diamond electrodes and generally found to be the largest in the case of glassy carbon. The voltammetry of IUPAC recommended potential scale reference systems, ferrocene/ferrocenium and cobaltocenium/cobaltocene, have been evaluated and found to be ideal in the case of the less viscous RTPILs but involve adsorption in the highly viscous ones. Other properties such as diffusion coefficients, ionic conductivity, and double layer capacitance also have been measured. The influence of water on the potential windows, viscosity, and diffusion has been studied systematically by deliberate addition of water to the dried ionic liquids. The survey highlights the problems with voltammetric studies in highly viscous room temperature protic ionic liquids and also suggests the way forward with respect to their possible industrial use.

Non-additivity of Faradaic and capacitance terms in ionic liquids

A study was conducted to evaluate the unexpected non-additivity of Faradaic and capacitance currents encountered in the case of ionic liquids. The results highlight that the non-additivity of Faradaic and capacitance currents should be considered in IL electrochemistry when multiple solutes are present.

The impact of ionic liquids on amyloid fibrilization of AB16-22 : tuning the rate of fibrilization using a reverse Hofmeister strategy

We have shown that the amyloid fibrilization of Aß16-22 follows a reverse hofmeister trend in pILs. Fast fibrilization rates of seconds can be achieved.

A facile, protic ionic liquid route to N-substituted 5-hydroxy-4-methyl-3- oxoisoindoline-1-carboxamides

Treatment of highly decorated bicyclo[2.2.1]heptadienes with the protic ionic liquid, TfOH:TEA effected quantitative conversion to the corresponding N-substituted 5-hydroxy-4-methyl-3-oxoisoindoline-1-carboxamides. This approach provides rapid access important chemical space for the rapid development of highly functionalised oxoisoindoline and is highly substrate tolerant.