Elucidation of the electrochemical oxidation pathway of ammonia in dimethylformamide and the room temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

The direct electrochemical oxidation of ammonia has been examined in both the organic solvent dimethylformamide (DMF) and the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIM][N(Tf)(2)]. The corresponding voltammetric responses have been shown to be similar in each solvent with a broad oxidative wave occurring upon the introduction of ammonia to the solution and the appearance of a new reductive wave following the oxidation. The oxidative reaction process has been examined and a suitable reaction pathway has been deduced, corresponding to the formation of ammonium cations after oxidation of the ammonia. A linear response of limiting current against vol% ammonia was observed in both DMF and [EMIM][N(Tf)(2)], suggesting potential application for analytical methods.

A structural and electrochemical investigation of 1-alkyl-3-methylimidazollum salts of the nitratodioxouranate(VI) anions [{UO2(NO3)(2)}(2)(mu(4)-C2O4)](2-), [UO2(NO3)(3)](-), and [UO2(NO3)(4)](2-)

The properties of the 1-butyl-3-methylimidazolium salt of the dinuclear mu(4)-(O,O,O',O'-ethane-1,2-dioato)bis[bis-(nitrato-O,O)dioxouranate(VI)] anion have been investigated using electrochemistry, single-crystal X-ray crystallography, and extended X-ray absorbance fine structure spectroscopy: the anion structures from these last two techniques are in excellent agreement with each other. Electrochemical reduction of the complex leads to the a two-electron metal-centered reduction of U(VI) to U(IV), and the production Of UO2, or a complex containing UO2. Under normal conditions, this leads to the coating of the electrode with a passivating film. The presence of volatile organic compounds in the ionic liquids 1-alkyl-3-methylimidazolium nitrate (where the 1-alkyl chain was methyl, ethyl, propyl, butyl, pentyl, hexyl, dodecyl, hexadecyl, or octadecyl) during the oxidative dissolution of uranium(IV) oxide led to the formation of a yellow precipitate. To understand the effect of the cation upon the composition and structure of the precipitates, 1-alkyl-3-methylimidazolium salts of a number of nitratodioxouranate(VI) complexes were synthesized and then analyzed using X-ray crystallography. It was demonstrated that the length of the 1-alkyl chain played an important role, not only in the composition of the complex salt, but also in the synthesis of dinuclear anions containing the bridging mu(4)-(O,O,O',O'-ethane-1,2-dioato), or oxalato, ligand, by protecting it from further oxidation.

Kinetic analysis of the reaction between electrogenerated superoxide and carbon dioxide in the room temperature ionic liquids 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and hexyltriethylammonium bis(trifluoromethylsulfonyl)imide

The reduction of oxygen in the presence of carbon dioxide has been investigated by cyclic voltammetry at a gold microdisk electrode in the two room-temperature ionic liquids 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide ([EMIM][N(Tf)(2)]) and hexyltriethylammonium bis(trifluoromethylsulfonyl)imide ([N-6222] [N(Tf)(2)]). With increasing levels of CO2, cyclic voltammetry shows an increase in the reductive wave and diminishing of the oxidative wave, indicating that the generated superoxide readily reacts with carbon dioxide. The kinetics of this reaction are investigated in both ionic liquids. The reaction was found to proceed via a DISP1 type mechanism in [EMIM][N(Tf)(2)] with an overall second-order rate constant of 1.4 +/- 0.4 x 10(3) M-1 s(-1). An ECE or DISP1 mechanism was determined to be the most likely pathway for the reaction in [N-6222][N(Tf)(2)], with an overall second-order rate constant of 1.72 +/- 0.45 x 10(3) m(-1) s(-1).

Determination of ammonia based on the electro-oxidation of hydroquinone in dimethylformamide or in the room temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

The results detail a novel methodology for the electrochemical determination of ammonia based on its interaction with hydroquinone in DMF. It has been shown that ammonia reversibly removes protons from the hydroquinone molecules, thus facilitating the oxidative process with the emergence of a new wave at less positive potentials. The analytical utility of the proposed methodology has been examined with a linear range from 10 to 95 ppm and corresponding limit-of-detection of 4.2 ppm achievable. Finally, the response of hydroquinone in the presence of ammonia has been examined in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluormethylsulfonyl)imide, [EMIM][N(Tf)(2)]. Analogous voltammetric waveshapes to that observed in DMF were obtained, thereby confirming the viability of the method in either DMF or [EMIM][N(Tf)(2)] as solvent. (C) 2003 Elsevier B.V. All rights reserved.

Voltammetry of oxygen in the room-temperature ionic liquids 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide and hexyltriethylammonium bis((trifluoromethyl)sulfonyl)imide: One-electron reduction to form superoxide. Steady-state and transient behavior in the same cyclic voltammogram resulting from widely different diffusion coefficients of oxygen and superoxide

The electrochemical reduction of oxygen in two different room-temperature ionic liquids, 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide ([EMIM][N(Tf)(2)]) and hexyltriethylammonium bis((trifluoromethyl)sulfonyl)imide ([N-6222][N(Tf)(2)]) was investigated by cyclic voltammetry at a gold microdisk electrode. Chronoamperometric measurements were made to determine the diffusion coefficient, D, and concentration, c, of the electroactive oxygen dissolved in the ionic liquid by fitting experimental transients to the Aoki model. [Aoki, K.; et al. J. Electroanal. Chem. 1981, 122, 19]. A theory and simulation designed for cyclic voltammetry at microdisk electrodes was then employed to determine the diffusion coefficient of the electrogenerated superoxide species, O-2(.-), as well as compute theoretical voltammograms to confirm the values of D and c for neutral oxygen obtained from the transients. As expected, the diffusion coefficient of the superoxide species was found to be smaller than that of the oxygen in both ionic liquids. The diffusion coefficients of O-2 and O-2(.-) in [N-6222][N(Tf)(2)], however, differ by more than a factor of 30 (D-O2 = 1.48 x 10(-10) m(2) s(-1), DO2.- = 4.66 x 10(-12) m(2) s(-1)), whereas they fall within the same order of magnitude in [EMIM][N(Tf)(2)] (D-O2 = 7.3 x 10(-10) m(2) s(-1), DO2.- = 2.7 x 10(-10) m(2) s(-1)). This difference in [N-6222][N(Tf)(2)] causes pronounced asymmetry in the concentration distributions of oxygen and superoxide, resulting in significant differences in the heights of the forward and back peaks in the cyclic voltammograms for the reduction of oxygen. This observation is most likely a result of the higher viscosity of [N-6222][N(Tf)(2)] in comparison to [EMIM][N(Tf)(2)], due to the structural differences in cationic component.

Ruthenium complexes of the 1,4-bis(diphenylphosphino)-1,3-butadiene-bridged diphosphine 1,2,3,4-Me-4-NUPHOS: Solvent-dependent interconversion of four- and six-electron donor coordination and transfer hydrogenation activity

In chloroform, [RuCl2(nbd)(py)(2)] (1) (nbd = norbornadiene; py = pyridine) reacts with 1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene (1,2,3,4-Me-4-NUPHOS) to give the dimer [Ru2Cl3(eta(4)-1,2,3,4-Me-4-NUPHOS)(2)]Cl (2a), whereas, in THF [RuCl2(1,2,3,4-Me-4-NUPHOS)(PY)(2)] (3) is isolated as the sole product of reaction. Compound 2 exists as a 4:1 mixture of two noninterconverting isomers, the major with C, symmetry and the minor with either C, or C-2 symmetry. A single-crystal X-ray analysis of [Ru2Cl3 (eta(4)-1,2,3,4-Me-4-NUPHOS)(2)] [SbF6] (2b), the hexafluoroantimonate salt of 2a, revealed that the diphosphine coordinates in an unusual manner, as a eta(4)-six-electron donor, bonded through both P atoms and one of the double bonds of the butadiene tether. Compounds 2a and 3 react with 1,2-ethylenediamine (en) in THF to afford [RuCl2(1,2,3,4-Me-4-NUPHOS)(en)] (4), which rapidly dissociates a chloride ligand in chloroform to give [RuCl(eta(4)-1,2,3,4-Me-4-NUPHOS)(en)] [Cl] (5a). Complexes 4 and 5a cleanly and quantitatively interconvert in a solvent-dependent equilibrium, and in THF 5a readily adds chloride to displace the eta(2)-interaction and re-form 4. A single-crystal X-ray structure determination of [RuCl(eta(4)-1,2,3,4-Me-4-NUPHOS)(en)][ClO4] (5b) confirmed that the diphosphine coordinates in an eta(4)-manner as a facial six-electron donor with the eta(2)-coordinated double bond occupying the site trans to chloride. The eta(4)-bonding mode can be readily identified by the unusually high-field chemical shift associated with the phosphorus atom adjacent to the eta(2)-coordinated double bond. Complexes 2a, 2b, 4, and 5a form catalysts that are active for transfer hydrogenation of a range of ketones. In all cases, catalysts formed from precursors 2a and 2b are markedly more active than those formed from 4 and 5a.

An EXAFS, X-ray diffraction, and electrochemical investigation of 1-alkyl-3-methylimidazolium salts of [{UO2(NO3)(2)}(2)(mu(4)-C2O4)](2-)

The structure of the 1-alkyl-3-methylimidazolium salts of the dinuclear mu(4)-(O,O,O',O'-ethane-1,2-dioato)-bis[bis(nitrato-O,O)dioxouranate(VI)] anion have been investigated using single crystal X-ray crystallography. In addition, EXAFS and electrochemical studies have been performed on the [C(4)mim](+) salt which is formed following the oxidative dissolution of uranium(IV) oxide in [C(4)mim][NO3]. EXAFS analysis of the solution following UO2 dissolution indicates a mixture of uranyl nitrate and mu(4)-(O,O,O',O'-ethane-1,2-dioato)-bis[bis(nitrato-O,O)dioxouranate(VI)] anions are formed.

A comparative study on the reactivity of electrogenerated bromine with cyclohexene in acetonitrile and the room temperature ionic liquid, 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide

The reactivity of electrogenerated bromine with cyclohexene has been studied on a platinum microelectrode by linear sweep and cyclic voltammetry in both the room temperature ionic liquid, 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, and the conventional aprotic solvent, acetonitrile. Variation in the voltammetric response was observed in the two solvents, indicating that the bromination reaction proceeded via separate mechanisms. To identify the different products, electrolysis was conducted on the preparative scale and NMR spectroscopy confirmed that while bromination of the organic substrate in the ionic liquid yields trans-1,2-dibromocyclohexane, in acetonitrile, trans-1-(N-acetylamino)-2-bromocyclohexane is instead obtained as the major product. The reaction mechanism for bromination in acetonitrile has been modeled using digital simulation.

Molecular layering and local order in thin films of 1-alkyl-3-methylimidazolium ionic liquids using X-ray reflectivity

X-ray reflectivity measurements in air of thin films of 1-alkyl-3-methylimidazolium salts in the liquid, liquid crystalline and solid states supported on Si( 111) are described. The films show Bragg features in both liquid crystalline and solid phases, but only after an initial annealing cycle. Kiessig fringes are observed only for the 1-octadecyl-3-methyl-imidazolium hexafluorophosphate films and, following analysis using Parratt32, a bi-layer model is proposed whereby the molecules are orientated with ionic groups at both salt-air and salt-silicon interfaces.

Crystal and liquid crystalline polymorphism in 1-alkyl-3-methylimidazolium tetrachloropalladate(II) salts

1-Alkyl-3-methylimidazolium tetrachloropalladate(ii) salts ([C-n-mim](2)[PdCl4], n = 10, 12, 14, 16, 18) containing a single, linear alkyl-chain substituent on the cation have been synthesised and their behaviour characterised by differential scanning calorimetry, polarising optical microscopy and small-angle X-ray scattering. The salts display thermotropic polymorphism, exhibiting both crystal-crystal transitions and, for n = 14-18, the formation of a thermotropic smectic liquid crystalline phase.

Effect of acetonitrile on the solubility of carbon dioxide in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide

The effect of the addition of acetonitrile on the solubility of carbon dioxide in an ionic liquid, the 1-ethyl-3- methylimidazolium bis(trifluoromethanesulfonyl)amide, [C(2)mim][NTf2], was studied experimentally at pressures close to atmospheric and as a function of temperature between 290 and 335 K. It was observed that the solubility of carbon dioxide decreases linearly with the mole fraction of acetonitrile from a value of 2.6 x 10(-2) in the pure ionic liquid at 303 K to a mole fraction of 1.3 x 10(-2) in the mixture [C(2)mim][NTf2] + CH3CN with x(CH3CN) = 0.77 at the same temperature. The gas solubility decreases with temperature, and the thermodynamic properties of solvation could be calculated. The vapor pressures of the [ C2mim][ NTf2] + CH3CN mixtures were measured in the same temperature range, and strong negative deviations from Raoult's law were obtained: up to 36% for a mixture with x(CH3CN) = 0.46 at 334 K. Negative excess molar volumes of approximately -1 cm(3) mol(-1) at equimolar composition could also be calculated from density measurements of the pure components and of the mixtures. These observations are confirmed by neutron diffraction studies and are compatible with the existence of strong ion-dipole interactions in the mixed liquid solvent.

Comment on the preparation of the ionic liquid 1-ethyl-3-methylimidazolium ethanoate: a unique monomeric, homoleptic pentacoordinate lead ethanoate complex

Atomic absorption spectroscopy of the ionic liquid 1-ethyl-3-methylimidazolium ethanoate ([emim](2)[O2CMe]), prepared according to International Patent WO 96/18459, showed it to contain large amounts of lead impurity: (ca. 0.5 M): [emim](2)[Pb(O2CMe)(4)] was isolated and shown crystallographically to contain the first known example of a monomeric, homoleptic pentacoordinate lead(ii) carboxylate complex, with a stereochemically active lone-pair.

Tris(1-ethyl-3-methylimidazolium) hexabromidoeuropate(III)

The crystal structure of the title compound, (C6H11N2)(3-)[EuBr6], consists of 1-ethyl-3-methylimidazolium cations and centrosymmetric octahedral hexabromidoeuropate anions. The [EuBr6](3-) anions are located at the corners and face-centres of the monoclinic unit cell. Characteristic hydrogen-bonding interactions can be observed between the bromide anions and the acidic H atoms of the imidazolium cations.

Green synthesis of ZnO nanoparticles in a room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Nanoparticles of ZnO with the wurtzite structure have been successfully synthesized via a microwave through the decomposition of zinc acetate dihydrate in an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, as a solvent. Fundamental characterizations including X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were conducted for the ZnO nanostructures.

Temperature Dependence of the Primary Relaxation in 1-Hexyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide

We present results from complementary characterizations of the primary relaxation rate of a room temperature ionic liquid (RTIL), 1-hexyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl} imide, [C(6)mim][Tf2N], over a wide temperature range. This extensive data set is successfully merged with existing literature data for conductivity, viscosity, and NMR diffusion coefficients thus providing, for the case of RTILs, a unique description of the primary process relaxation map over more than 12 decades in relaxation rate and between 185 and 430 K. This unique data set allows a detailed characterization of the VTF parameters for the primary process, that are: B = 890 K, T-0 = 155.2 K, leading to a fragility index m = 71, corresponding to an intermediate fragility. For the first time neutron spin echo data from a fully deuteriated sample of RTIL at the two main interference peaks, Q = 0.76 and 1.4 angstrom(-1) are presented. At high temperature (T > 250 K), the collective structural relaxation rate follows the viscosity behavior; however at lower temperatures it deviates from the viscosity behavior, indicating the existence of a faster process.