P 1‐Butyl‐3‐methylimidazolium tetrafluoroborate 1‐Butyl‐3‐methylimidazolium hexafluorophosphate R 1‐Butyl‐3‐methylimidazolium chloride Potassium hexafluorophosphate P 1‐Butyl‐3‐methylimidazolium hexafluorophosphate
The nature of the interactions between 1,3-dialkylimidazolium cations and noncoordinating anions such as tetrafluoroborate, hexafluorophosphate, and tetraphenylborate has been studied in the solid state by X-ray diffraction analysis and in solution by (1)H NMR spectroscopy, conductivity, and microcalorimetry. In the solid state, these compounds show an extended network of hydrogen-bonded cations and anions in which one cation is surrounded by at least three anions and one anion is surrounded by at least three imidazolium cations. In the pure form, imidazolium salts are better described as polymeric supramolecules of the type {[(DAI)(3)(X)](2+)[(DAI)(X)(3)](2-)}(n) (where DAI is the dialkylimidazolium cation and X is the anion) formed through hydrogen bonds of the imidazolium cation with the anion. In solution, this supramolecular structural organization is maintained to a great extent, at least in solvents of low dielectric constant, indicating that mixtures of imidazolium ionic liquids with other molecules can be considered as nanostructured materials. This model is very useful for the rationalization of the majority of the unusual behavior of the ionic liquids.
Electrospray ionization mass spectrometry (ESI-MS) is found to gently and efficiently transfer small to large as well as singly to multiply charged [X+]n[A-]m supramolecules of imidazolium ion (X+) ionic liquids to the gas phase, and to reveal "magic numbers" for their most favored assemblies. Tandem mass spectrometric experiments (ESI-MS/MS) were then used to dissociate, via low-energy collision activation, mixed and loosely bonded [A- - - -X- - - -A']- and [X- - - -A- - - -X']+ gaseous supramolecules, as well as their higher homologues, and to estimate and order via Cooks' kinetic method (CKM) and B3LYP/6-311G(d,p) calculations the intrinsic solvent-free magnitude of hydrogen bonds. For the five anions studied, the relative order of intrinsic hydrogen-bond strengths to the 1-n-butyl-3-methylimidazolium ion [X1]+ is: CF3CO2- (zero) > BF4- (-3.1) > PF6- (-10.0) > InCl4- (-16.4) and BPh4- (-17.6 kcal mol(-1)). The relative hydrogen-bond strength for InCl4- was measured via CKM whereas those for the other anions were calculated and used as CKM references. A good correlation coefficient (R=0.998) between fragment ion ratios and calculated hydrogen-bond strengths and an effective temperature (Teff) of 430 K demonstrate the CKM reliability for measuring hydrogen-bond strengths in gaseous ionic liquid supramolecules. Using CKM and Teff of 430 K, the intrinsic hydrogen-bond strengths of BF4- for the three cations investigated is: 1-n-butyl-3-methyl-imidazolium ion (0) > 1,3-di-[(R)-3-methyl-2-butyl]-imidazolium ion (-2.4) > 1,3-di-[(R)-alpha-methylbenzyl]-imidazolium ion (-3.0 kcal mol(-1)). As evidenced by "magic" numbers, greater stabilities are found for the [(X1)2(BF4)3]- and [(X1)5A4]+ supramolecules (A not equal InCl4-).
Líquidos iônicos, em particular aqueles derivados do cátion 1,3-dialquilimidazólio, que possuem uma ampla faixa de temperatura em suas fases líquidas, pressões de vapores muito pequenas, baixas viscosidades e elevada estabilidade térmica e química vêm emergindo como uma nova classe de solventes "verdes" para processos de extração e separação, síntese orgânica e catálise. Os principais resultados obtidos com estes líquidos em Química Limpa nos últimos dois anos são objeto deste artigo de revisão. Ionic liquids, especially those based on the 1,3-dialkylimidazolium cation, with a large range of liquid phase, negligible vapour pressure, low viscosity and high thermal and chemical stability are emerging as a new class of 'green' solvents for extraction and separation processes, organic synthesis and catalysis. The main milestones reached in the last two years, on the use of ionic liquids in green technologies, are reviewed.
In the Heck reaction between aryl halides and n-butyl acrylate, the palladacycle {Pd[kappa(1)-C, kappa(1)-N-C=(C(6)H(5))C(Cl)CH(2)NMe(2)](mu-Cl)}(2), 1, is merely a reservoir of the catalytically active Pd(0) species [1](Pd colloids or highly active forms of low ligated Pd(0) species) that undergoes oxidative addition of the aryl halide on the surface with subsequent detachment, generating homogeneous Pd(II) species. The main catalytic cycle is initiated by oxidative addition of iodobenzene to [1], followed by the reversible coordination of the olefin to the oxidative addition product. All the unimolecular subsequent steps are indistinguishable kinetically and can be combined in a single step. This kinetic model predicts that a slight excess of alkene relative to iodobenzene leads to a rapid rise in the Pd(0) concentration while when using a slight excess of iodobenzene, relative to alkene, the oxidative addition product is the resting state of the catalytic cycle. Competitive experiments of various bromoarenes and iodoarenes with n-butyl acrylate catalyzed by 1 and CS, CP, and NCN palladacycles gave the same rho value (2.4-2.5 for Ar-Br and 1.7-1.8 for Ar-I) for all palladacycles employed, indicating that they generate the same species in the oxidative addition step. The excellent fit of the slope with the sigma(0) Hammett parameter and the entropy of activation of -43 +/- 8 J mol(-1) K(-1) are consistent with an associative process involving the development of only a partial charge in the transition state for the oxidative step of iodobenzene.
A janela eletroquímica do líquido iônico trifluoroacetato de 1-n-butil-3-metilimidazólio foi estudada sobre eletrodos de carbono vítreo e platina em condições estática e dinâmica. Observouse uma drástica diminuição da janela eletroquímica ao trocar o eletrodo de carbono vítreo (4.50 V) pelo de platina (2.50 V). A variação da velocidade de rotação do eletrodo e da velocidade de varredura não afetaram o perfil dos voltamogramas, porém alteraram as densidades de corrente dos picos referentes aos processos anódicos e catódicos. A adsorção do cátion imidazólio durante o processo de transferência de carga na região catódica foi evidenciada, principalmente para baixas velocidades de rotação do eletrodo.The 1-n-butyl-3-methylimidazolium trifluoroacetate ionic liquid electrochemical windows have been investigated at vitreous carbon and platinum disc electrodes under static and dynamic conditions. The electrochemical window abruptly decreases by changing vitreous carbon (4.50 V) by platinum electrode (2.50 V). Electrode rotation and potential sweep rate did not affect the current-potential profiles but alter the current values of both anodic and cathodic peaks. The adsorption of imidazolium cation involved in the charge transfer process during the cathodic sweep rate was evidenced, mainly at low electrode rotation.Keywords: platinum electrode, vitreous carbon electrode, ionic liquid, imidazolium cation IntroductionRoom temperature molten salts or ionic liquids have been historically considered as liquid electrolytes composed entirely of ions. However, new evidences in the last years pointed out that these compounds, specially those based upon N,N'-dialkyl substituted imidazolium cations, are better described as liquid compounds that display ioniccovalent structures.1 In the light of their promising physical and chemical properties, room temperature ionic liquid systems attract increasing attention for applications as solvents in organic synthesis, transition metal two-phase catalysis, liquid-liquid extraction and electrochemical devices.1-3 Some characteristics that make these liquids so versatile and promising as novel solvents are (i) the high thermal stability and wide range of liquid phase, 4 (ii) their ability to act as solvents for many organic and inorganic materials, since it has been shown that they have micro heterogeneities that induce to act either as highly or weakly polar liquids, 5 (iii) the considerable conductivity, which commends their use in the study of electrochemical processes without using supporting electrolytes, and (iv) the negligible vapor pressure in contrast with conventional organic solvents, permitting their study under conditions of high vacuum. From the ecological point of view, the easier recovery of these solvents and its negligible vapor pressure, which avoid vapor emissions, makes these solvents environmental friendly. 1We have recently showed that the ionic liquids obtained from the combination of 1-n-butyl-3-methylimidazolium cation with tetrafluoroborate and hexafluorophosphate are ...
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