- A magnetic ionic liquid based on tetrachloroferrate exhibits three-dimensional magnetic ordering: A combined experimental and theoretical study of the magnetic interaction mechanism
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A new magnetic ionic liquid (MIL) with 3D antiferromagnetic ordering has been synthetized and characterized. The information obtained from magnetic characterization was supplemented by analysis of DFT calculations and the magneto-structural correlations. The result gives no evidence for direct iron-iron interactions, corroborating that the 3D magnetic ordering in MILs takes place via super-exchange coupling containing two diamagnetic atoms intermediaries. Liquid attraction: The crystal structure, DFT calculations and magnetic properties of a new magnetic ionic liquid (MIL), Dimim[FeCl 4], which displays 3 D magnetic ordering below 6 K, is presented. The study of its magnetostructural correlations points to the relative importance of two influential factors on the strength of the magnetic interaction of MILs: the spin population into the metal complex anion and the distances and angles between the superexchange pathways, type M-X-X-M (M=Metal and X=halide). Copyright
- Garcia-Saiz, Abel,Migowski, Pedro,Vallcorba, Oriol,Junquera, Javier,Blanco, Jesus Angel,Gonzalez, Jesus Antonio,Fernandez-Diaz, Maria Teresa,Rius, Jordi,Dupont, Jairton,Rodriguez Fernandez, Jesus,De Pedro, Imanol
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- Reactions of Imidazolio-Phosphides with Organotin Chlorides: Surprisingly Diverse
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Reactions of primary imidazolio-phosphides (“imidazolylidene-phosphinidenes”) with R2SnCl2 yield as main products spectroscopically detectable Lewis pairs which undergo base-induced dehydrochlorination in the presence of excess dichlorostannane to afford zwitterionic chloride adducts of distannylated imidazolio-phosphines. In contrast, reactions with R3SnCl proceed under dismutation to furnish mixtures containing imidazolium salts and stannylated (oligo)phosphines P(SnR3)3 and P7(SnR3)3, respectively. DFT studies were used to rationalize the divergent behavior based on the presumption that the reactions proceed under thermodynamic control and the products observed represent the most stable species under the specific reaction conditions. Computational simulation of selected reaction steps provides a model mechanism for Lewis-acid promoted creation of PP-bonds, which is a prerequisite for oligophosphine formation. The computational studies further highlight parallels between reactions of imidazolio-phosphides with Lewis and Br?nsted acids, and allow also to extrapolate the behavior of the P-nucleophiles towards other electrophiles than organotin chlorides.
- Goerigk, Florian,Birchall, Nicholas,Feil, Christoph M.,Nieger, Martin,Gudat, Dietrich
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- Mechanism studies of oxidation and hydrolysis of Cu(I)–NHC and Ag–NHC in solution under air
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The decomposition of copper(I)–NHC and silver-NHC complexes in solution under air was studied. The Cu(I)–NHCs were oxidized into urea derivatives and hydrolysed into imidazoliums or benzimidazoliums. The decomposition of Ag–NHC with a saturated backbone led to ring-opening product, while the Ag–NHC with an unsaturated backbone led to imidazolium and Ag-bisNHC complex. The effects of steric property, hydrophilicity, and binding energy of NHC to O2 and H2O on the decomposition of Cu(I)–NHC were studied using theoretical calculations. Steric hindrance played an important role on the stability of Cu(I)–NHC. Pathways for the decomposition of Cu(I)–NHC and Ag–NHC were proposed.
- Li, Dazhi,Ollevier, Thierry
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supporting information
(2019/11/29)
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- Synthesis of Imidazolidinone, Imidazolone, and Benzimidazolone Derivatives through Oxidation Using Copper and Air
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A new synthetic method of urea derivatives using copper and air was developed. These mild conditions provided moderate to very good yields for 15 examples (53-93%), while low yields were obtained with sterically hindered substrates (3 examples). The reaction was found to go through an in situ generated copper-N-heterocyclic carbene, which was then oxidized into cyclic urea derivatives possessing alkyl, benzyl, aryl, hydroxy, Boc-protected, and tertiary amine groups.
- Li, Dazhi,Ollevier, Thierry
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supporting information
p. 3572 - 3575
(2019/05/24)
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- N-Heterocyclic Carbene Boranes as Reactive Oxygen Species-Responsive Materials: Application to the Two-Photon Imaging of Hypochlorous Acid in Living Cells and Tissues
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N-Heterocyclic carbene (NHC) boranes undergo oxidative hydrolysis to give imidazolium salts with excellent kinetic selectivity for HOCl over other reactive oxygen species (ROS), including peroxides and peroxynitrite. Selectivity for HOCl results from the
- Pak, Yen Leng,Park, Sang Jun,Wu, Di,Cheon, BoHyun,Kim, Hwan Myung,Bouffard, Jean,Yoon, Juyoung
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p. 1567 - 1571
(2018/01/15)
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- A design of experiment approach for ionic liquid-based extraction of toxic components-minimized essential oil from Myristica fragrans houtt
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The effect of the addition of ionic liquids (ILs) during the hydrodistillation of Myristica fragrans Houtt. (nutmeg) essential oil was studied. The essential oil of M. fragrans is characterized by the presence of terpenes, terpenoids, and of phenylpropanoids, such as methyl eugenol and safrole, that are regarded as genotoxic and carcinogenic. The aim of the work was to determine the best ionic liquid to improve the yield of the extraction of M. fragrans essential oil and decrease the extraction of toxic phenylpropanoids. Six ILs, namely 1,3-dimethylimidazolium chloride (1), 1,3-dimethylimidazolium dimethylphosphate (2), 1-(2-hydroxyethyl)-3-methylimidazolium chloride (3), 1-(2-hydroxyethyl)-3-methylimidazolium dimethylphosphate (4), 1-butyl-3-methylimidazolium chloride (5), and 1-butyl-3-methylimidazolium dimethylphosphate (6), were prepared by previously reported, innovative methods and then tested. An experimental design was used to optimize the extraction yield and to decrease the phenylpropanoids percentage using the synthesized ILs. The influence of the molarity of ILs was also studied. MODDE 12 software established 0.5 M 1-butyl-3-methylimidazolium chloride as the best co-solvent for the hydrodistillation of M. fragrans essential oil.
- Lanari, Daniela,Marcotullio, Maria Carla,Neri, Andrea
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- Ionic liquid preparation method, ionic liquid and applications of ionic liquid in preparation of separation membranes
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The invention relates to an ionic liquid preparation method, particularly to an imidazole-based ionic liquid preparation method and a prepared ionic liquid thereof, and applications of the ionic liquid in preparation of separation membranes. The invention provides an ionic liquid preparation method, wherein reactants react in a reaction container to synthesize an ionic liquid, and are imidazole or a substituent-containing imidazole, a hydrogen chloride gas and a carbonate, and the hydrogen chloride gas is introduced into the reaction container from the bottom portion of the reaction container from bottom to top. According to the present invention, the prepared imidazole-based ionic liquid has characteristics of simple synthesis method and low cost; and the synthesized imidazole-based ionic liquid has characteristics of low water content and high purity, and meets the requirement of industrial large-scale production.
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Paragraph 0039; 0040
(2018/03/01)
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- Photochemistry of imidazolium cations. Water addition to methylimidazolium ring induced by UV radiation in aqueous solution
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The UV-C induced photoaddition of water to N-alkyl-N′-methylimidazolium cations was studied. The main photoreaction products exhibit chemical additions of a proton and a hydroxyl group to either positions 4 or 5 of the imidazolium ring. For unsymmetrical imidazolium cations, two positional isomers were obtained as products. In these cases, the most abundant isomer is the one in which the hydroxyl group adds at the side of the ring having the longer alkyl substituent. Experiments performed in D2O solutions reveal that the additions of proton and hydroxyl group never take place at the same carbon atom, in a reaction that produces equal amounts of diastereoisomers. Moreover, the formation of diastereoisomers at equal proportions suggests that the reaction proceeds in an unconcerted fashion.
- Sarmiento, Gabriela P.,Zelcer, Andrés,Espinosa, Mariela S.,Babay, Paola A.,Mirenda, Martin
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p. 155 - 163
(2015/09/21)
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- Synthesis of tridentate 2,6-bis(imino)pyridyl ruthenium(II) complexes with n-heterocyclic carbene ligands: Activation of imidazolium salts
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Low-valent Ru(0) complexes, [η2-N3]Ru(η6-Ar) (1) or {[N3]Ru}2(μ-N2) (2), where Ar = C6H6 or C6H5Me, and [N3] = 2,6-(2,4,6-(CH3/s
- Yoo, Hyojong,Berry, Donald H.
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p. 11447 - 11456
(2015/01/16)
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- Synthesis, limitations, and thermal properties of energetically- substituted, protonated imidazolium picrate and nitrate salts and further comparison with their methylated analogs
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The possibility of forming simple energetic ionic liquids via the straightforward protonation of heterocyclic amines with nitric or picric acid was explored with 1-alkylimidazoles, 1-alkyl-2-methylimidazoles, and nitro, dinitro, and dicyano-substituted derivatives. The melting points of most of the prepared salts were lower than expected and of the 30 compounds prepared, more than half were found to melt below 100 °C. Limitations in the approach were found as a result of the use of energetic electron withdrawing substituents, such as nitro or cyano, which results in a reduction in nucleophilicity of the heterocycle and an inability to form salts with the acids studied. Interesting thermal behavior was observed with several of the new salts including supercooling and crystallization on heating. Comparison of the simple protonated imidazolium nitrate and picrate salts with their methylated analogs indicated that the protonated ionic liquids do not differ substantially in their melting points from the methylated analogs. However, the thermal stabilities of protonated imidazolium salts are much lower than their alkylated derivatives. Nitrate salts with alkylated cations tend to be more thermally stable than the corresponding picrate salts, but with protonated cations, the picrate salts tend to be approximately 70-80 °C more stable than the nitrate salts. Moreover, accelerating rate calorimetry (ARC) revealed that alkylated salts decompose much less exothermically (in some cases endothermically) than the protonated analogs, and that among all the analyzed salts, the most energetic materials found were protonated 1-methylimidazolium nitrate and 1,2-dimethylimidazolium picrate. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012.
- Smiglak, Marcin,Hines, C. Corey,Reichert, W. Matthew,Vincek, Adam S.,Katritzky, Alan R.,Thrasher, Joseph S.,Sun, Luyi,McCrary, Parker D.,Beasley, Preston A.,Kelley, Steven P.,Rogers, Robin D.
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experimental part
p. 702 - 722
(2012/05/04)
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- A simple halide-to-anion exchange method for heteroaromatic salts and ionic liquids
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A broad and simple method permitted halide ions in quaternary heteroaromatic and ammonium salts to be exchanged for a variety of anions using an anion exchange resin (A- form) in non-aqueous media. The anion loading of the AER (OH- form) was examined using two different anion sources, acids or ammonium salts, and changing the polarity of the solvents. The AER (A- form) method in organic solvents was then applied to several quaternary heteroaromatic salts and ILs, and the anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Relying on the hydrophobicity of the targeted ion pair for the counteranion swap, organic solvents with variable polarity were used, such as CH3OH, CH3CN and the dipolar nonhydroxylic solvent mixture CH3CN:CH2Cl 2 (3:7) and the anion exchange was equally successful with both lipophilic cations and anions.
- Alcalde, Ermitas,Dinares, Immaculada,Ibanez, Anna,Mesquida, Neus
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experimental part
p. 4007 - 4027
(2012/07/28)
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- An efficient ultrasonic-assisted synthesis of imidazolium and pyridinium salts based on the Zincke reaction
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A mild and efficient method has been developed using ultrasound irradiation for the synthesis of imidazolium and pyridinium salts based on the Zincke reaction. Tertiary nitrogen nucleophiles such as pyridines and imidazoles can be alkylated with primary amine by simply using their ammonium form Zincke salts. In almost all cases, a clear yield increase results and a dramatic reduction of the reaction time accompanied by an improved quality of the products occurs.
- Zhao, Sanhu,Xu, Xiaoming,Zheng, Lu,Liu, Hai
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experimental part
p. 685 - 689
(2011/02/23)
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- A novel and green method for the synthesis of ionic liquids using the corresponding acidic ionic liquid precursors and dialkyl carbonate
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A novel and green method for the synthesis of dialkylimidazolium ionic liquids (ILs) has been developed. It was through a one-step alkylation of dialkyl carbonate with the corresponding acidic ionic liquid precursors (AILPs) prepared from the neutralization of imidazole derivatives with acids.
- Xiao, Wenjun,Wang, Xiaoxing,Chen, Qin,Wu, Tinghua,Wu, Ying,Dai, Lizong,Song, Chunshan
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supporting information; experimental part
p. 1112 - 1113
(2011/08/08)
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- Imidazolium ionic liquids: A simple anion exchange protocol
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An efficient and simple protocol was developed to obtain quantitative iodide or bromide exchange for a broad range of anions in imidazolium ionic liquids. Selected anions were loaded in an anion exchange resin using two different procedures and were then used to provide a pure convenient ion pair. The Royal Society of Chemistry 2009.
- Dinares, Immaculada,Garcia De Miguel, Cristina,Ibanez, Anna,Mesquida, Neus,Alcalde, Ermitas
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supporting information; experimental part
p. 1507 - 1510
(2010/06/11)
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- Lonization state and ion migration mechanism of room temperature molten dialkylimidazolium fluorohydrogenates
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The ionization state of room temperature molten salts, alkylimidazolium fluorohydrogenates (RMIm-(HF)2.3F: R = alkyl group, M =methyl group), was evaluated from the observed diffusion coefficient and viscosity, using the Stokes-Einstein relation. Assuming that the dissociation degree of the salt is acceptable for representation of the ionic state of the molten salts, the larger the cation size with elongation of the alkyl chain was, the higher the dissociation degree of the salt Further, we proposed that an idea of the "degree of ordering of cations and anions" was more suitable to represent the ionization state without solvent species. On the basis of this idea, the smaller the cation size of RMIm(HF)2.3F salt was, the higher the ordering of the ion, indicating formation of domain particles of aggregated ions as a unit of mobile species such as A(AX)m + and X(AX)n- for A+X- salt. It was found that highly ordered particles, with large numbers for m and n, showed a high diffusion coefficient. ? 2005 American Chemical Society.
- Saito, Yuria,Hirai, Kenichi,Matsumoto, Kazuhiko,Hagiwara, Rika,Minamizaki, Yoshihiro
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p. 2942 - 2948
(2007/10/03)
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- Convenient and general synthesis of symmetrical N,N'-disubstituted imidazolium halides
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N,N-Dialkyl- and N,N-dibenzylimidazolium chlorides or bromides were synthesized in high yield from the appropriate primary alkyl or benzyl halide and N-trimethylsilylimidazole.
- Harlow, Karsten J.,Hill, Anthony F.,Welton, Tom
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p. 697 - 698
(2007/10/03)
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