Regioselectivitat en l'orto-carborà : mono- i multisubstitució : clústers de bor en líquids iònics /

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Synthesis, structural, spectroscopic and electrochemical studies of carborane substituted naphthyl selenides

[EN] New unsymmetrical selenides bearing an o-carborane and a naphthalene ring as the substituents were prepared by the cleavage of the corresponding diselenides. The compounds were characterized by means of spectroscopic and analytical methods. Se-77 NMR signals of the selenium atoms attached to the carbon atoms of the carborane cages are shifted downfield in comparison to those bonded only to the aromatic rings, indicating an electron withdrawing effect of the o-carboranyl substituent. Compounds 1-(2-R-1,2-dicarba-closo-carboranyl)naphthyl selenides (R = Me, 1; Ph, 2) were characterized by means of single crystal X-ray diffraction. The influence of the electronic nature of the substituents attached to the selenium atoms on the structural parameters and packing properties of naphthyl selenides are discussed. Theoretical calculations and cyclic voltammetry (CV) studies were carried out to compare the bonding nature of carboranyl and analogous aryl selenium compounds. Cyclic voltammetry studies of naphthyl carboranyl mono and diselenides have shown that the carboranyl fragment polarizes the Se lone pair making it less prone to generate a Se-Se bond.This work was supported by the Japan-Spain Research Cooperative Program, Joint Project, 2004JP0102 from Japan Society for the Promotion of Science (JSPS) and CSIC, CICYT (CTQ2010-16237) and the Generalitat de Catalunya, 2009/SGR/00279. Dr O. Guzyr is grateful to Ministerio Education, Cultura y Deporte for grant SAB2003-0122.Guzyr, O.; Viñas, C.; Wada, H.; Hayashi, S.; Nakanishi, W.; Teixidor, F.; Vaca Puga, A.... (2011). Synthesis, structural, spectroscopic and electrochemical studies of carborane substituted naphthyl selenides. Dalton Transactions. 40(13):3402-3411. https://doi.org/10.1039/c0dt01658fS34023411401

Copper-doped titania photocatalysts for simultaneous reduction of CO2 and production of H-2 from aqueous sulfide

Copper-doped titanium dioxide materials with anatase phase (Cu-TiO2, atomic Cu contents ranging from 0 to 3% relative to the sum of Cu and Ti), and particle sizes of 12-15 nm, were synthesised by a solvo-thermal method using ethanol as the solvent and small amounts of water to promote the hydrolysiscondensation processes. Diffuse reflectance UV-vis spectroscopy show that the edges of absorption of the titania materials are somewhat shifted to higher wavelengths due to the presence of Cu. X-ray photoelectron spectroscopy (XPS) indicate that Cu(II) is predominant. Photocatalytic CO2 reduction experiments were performed in aqueous Cu-TiO2 suspensions under UV-rich light and in the presence of different solutes. Sulfide was found to promote the efficient production of H-2 from water and formic acid from CO2. The effect of the Cu content on the photoactivity of Cu-TiO2 was also studied, showing that copper plays a role on the photocatalytic reduction of CO2.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2012-32315) is gratefully acknowledged. F.G. and B.J.-L. are thankful for financial support from Spanish Government (AP2010-2748 PhD grant and MAT2011-27008 project) and Jaume I University (P1 1B2014-21 project). SCIC from Jaume I University and Servicio de Microscopia Electronica at Universitat Politecnica de Valencia are also acknowledged for instrumental facilities. A.V.P. is grateful to both the Consejo Superior de Investigaciones Cientifficas (CSIC) and the European Social Fund (ESF) for a JAE-Doc postdoctoral grant. Lichen Liu is gratefully acknowledged for assistance in recording HRTEM images.Gonell-Gómez, F.; Puga Vaca, A.; Julián López, B.; García Gómez, H.; Corma Canós, A. (2016). Copper-doped titania photocatalysts for simultaneous reduction of CO2 and production of H-2 from aqueous sulfide. Applied Catalysis B: Environmental. 180:263-270. https://doi.org/10.1016/j.apcatb.2015.06.019S26327018

Carbon dioxide uptake from natural gas by binary ionic liquid water mixtures

[EN] Carbon dioxide solubility in a set of carboxylate ionic liquids formulated with stoicheiometric amounts of water is found to be significantly higher than for other ionic liquids previously reported. This is due to synergistic chemical and physical absorption. The formulated ionic liquid/water mixtures show greatly enhanced carbon dioxide solubility relative to both anhydrous ionic liquids and aqueous ionic liquid solutions, and are competitive with commercial chemical absorbers, such as activated N-methyldiethanolamine or monoethanolamine.The authors would like to acknowledge PETRONAS for financial support of this research, and Cytec (especially Dr Al Robertson) for supplying some of the phosphonium ionic liquids used.Anderson, K.; Atkins, MP.; Estager, J.; Kuah, Y.; Ng, S.; Oliferenko, AA.; Plechkova, NV.... (2015). Carbon dioxide uptake from natural gas by binary ionic liquid water mixtures. 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G.Compton and C.Hardacre, Chloride Determination in Ionic Liquids, in Ionic Liquids IIIB: Fundamentals, Progress, Challenges, and Opportunities - Transformations and Processes, ed. R. D. Rogers and K. R. Seddon, ACS Symp. Ser., Vol. 902, American Chemical Society, Washington D.C., 2005, vol. 902, pp. 244–258J. L. Anthony , E. J.Maginn and J. F.Brennecke, Gas Solubilities in 1-n-Butyl-3-methylimidazolium Hexafluorophosphate, in Ionic Liquids: Industrial Applications to Green Chemistry, ed. R. D. Rogers and K. R. Seddon, ACS Symp. Ser, Vol. 818, American Chemical Society, Washington D.C., 2002, vol. 818, pp. 260–269J. H. Davis Jr. , Working Salts: Syntheses and Uses of Ionic Liquids Containing Functionalized Ions, in Ionic Liquids: Industrial Applications to Green Chemistry, ed. R. D. Rogers and K. R. Seddon, ACS Symp. Ser, Vol. 818, American Chemical Society, Washington D.C., 2002, vol. 818, pp. 247–259Bates, E. D., Mayton, R. D., Ntai, I., & Davis, J. H. (2002). CO2Capture by a Task-Specific Ionic Liquid. Journal of the American Chemical Society, 124(6), 926-927. doi:10.1021/ja017593dWang, C., Luo, X., Zhu, X., Cui, G., Jiang, D., Deng, D., … Dai, S. (2013). The strategies for improving carbon dioxide chemisorption by functionalized ionic liquids. RSC Advances, 3(36), 15518. doi:10.1039/c3ra42366bRamdin, M., de Loos, T. W., & Vlugt, T. J. H. (2012). State-of-the-Art of CO2Capture with Ionic Liquids. Industrial & Engineering Chemistry Research, 51(24), 8149-8177. doi:10.1021/ie3003705Zhang, X., Zhang, X., Dong, H., Zhao, Z., Zhang, S., & Huang, Y. (2012). Carbon capture with ionic liquids: overview and progress. Energy & Environmental Science, 5(5), 6668. doi:10.1039/c2ee21152aYokozeki, A., & Shiflett, M. B. (2009). Separation of Carbon Dioxide and Sulfur Dioxide Gases Using Room-Temperature Ionic Liquid [hmim][Tf2N]. Energy & Fuels, 23(9), 4701-4708. doi:10.1021/ef900649cCabaço, M. I., Besnard, M., Danten, Y., & Coutinho, J. A. P. (2012). Carbon Dioxide in 1-Butyl-3-methylimidazolium Acetate. I. Unusual Solubility Investigated by Raman Spectroscopy and DFT Calculations. The Journal of Physical Chemistry A, 116(6), 1605-1620. doi:10.1021/jp211211nCarvalho, P. J., Álvarez, V. H., Schröder, B., Gil, A. M., Marrucho, I. M., Aznar, M., … Coutinho, J. A. P. (2009). Specific Solvation Interactions of CO2on Acetate and Trifluoroacetate Imidazolium Based Ionic Liquids at High Pressures. The Journal of Physical Chemistry B, 113(19), 6803-6812. doi:10.1021/jp901275bGoodrich, B. F., de la Fuente, J. C., Gurkan, B. E., Zadigian, D. J., Price, E. A., Huang, Y., & Brennecke, J. F. (2011). Experimental Measurements of Amine-Functionalized Anion-Tethered Ionic Liquids with Carbon Dioxide. Industrial & Engineering Chemistry Research, 50(1), 111-118. doi:10.1021/ie101688aGoodrich, B. F., de la Fuente, J. C., Gurkan, B. E., Lopez, Z. K., Price, E. A., Huang, Y., & Brennecke, J. F. (2011). Effect of Water and Temperature on Absorption of CO2by Amine-Functionalized Anion-Tethered Ionic Liquids. The Journal of Physical Chemistry B, 115(29), 9140-9150. doi:10.1021/jp2015534Ferguson, J. L., Holbrey, J. D., Ng, S., Plechkova, N. V., Seddon, K. R., Tomaszowska, A. A., & Wassell, D. F. (2011). A greener, halide-free approach to ionic liquid synthesis. Pure and Applied Chemistry, 84(3), 723-744. doi:10.1351/pac-con-11-07-21Shiflett, M. B., Kasprzak, D. J., Junk, C. P., & Yokozeki, A. (2008). Phase behavior of {carbon dioxide+[bmim][Ac]} mixtures. The Journal of Chemical Thermodynamics, 40(1), 25-31. doi:10.1016/j.jct.2007.06.003Shiflett, M. B., & Yokozeki, A. (2009). Phase Behavior of Carbon Dioxide in Ionic Liquids: [emim][Acetate], [emim][Trifluoroacetate], and [emim][Acetate] + [emim][Trifluoroacetate] Mixtures. Journal of Chemical & Engineering Data, 54(1), 108-114. doi:10.1021/je800701jShiflett, M. B., Drew, D. W., Cantini, R. A., & Yokozeki, A. (2010). Carbon Dioxide Capture Using Ionic Liquid 1-Butyl-3-methylimidazolium Acetate. Energy & Fuels, 24(10), 5781-5789. doi:10.1021/ef100868aCabaço, M. I., Besnard, M., Danten, Y., & Coutinho, J. A. P. (2011). Solubility of CO2in 1-Butyl-3-methyl-imidazolium-trifluoro Acetate Ionic Liquid Studied by Raman Spectroscopy and DFT Investigations. The Journal of Physical Chemistry B, 115(13), 3538-3550. doi:10.1021/jp111453aGurau, G., Rodríguez, H., Kelley, S. P., Janiczek, P., Kalb, R. S., & Rogers, R. D. (2011). Demonstration of Chemisorption of Carbon Dioxide in 1,3-Dialkylimidazolium Acetate Ionic Liquids. Angewandte Chemie International Edition, 50(50), 12024-12026. doi:10.1002/anie.201105198Besnard, M., Cabaço, M. I., Vaca Chávez, F., Pinaud, N., Sebastião, P. J., Coutinho, J. A. P., … Danten, Y. (2012). CO2 in 1-Butyl-3-methylimidazolium Acetate. 2. NMR Investigation of Chemical Reactions. The Journal of Physical Chemistry A, 116(20), 4890-4901. doi:10.1021/jp211689zJaniczek, P., Kalb, R. S., Thonhauser, G., & Gamse, T. (2012). Carbon dioxide absorption in a technical-scale-plant utilizing an imidazolium based ionic liquid. Separation and Purification Technology, 97, 20-25. doi:10.1016/j.seppur.2012.03.003Ober, C. A., & Gupta, R. B. (2012). pH Control of Ionic Liquids with Carbon Dioxide and Water: 1-Ethyl-3-methylimidazolium Acetate. Industrial & Engineering Chemistry Research, 51(6), 2524-2530. doi:10.1021/ie201529dStevanovic, S., Podgoršek, A., Pádua, A. A. H., & Costa Gomes, M. F. (2012). Effect of Water on the Carbon Dioxide Absorption by 1-Alkyl-3-methylimidazolium Acetate Ionic Liquids. The Journal of Physical Chemistry B, 116(49), 14416-14425. doi:10.1021/jp3100377Stevanovic, S., Podgorsek, A., Moura, L., Santini, C. C., Padua, A. A. H., & Costa Gomes, M. F. (2013). Absorption of carbon dioxide by ionic liquids with carboxylate anions. 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Acta Crystallographica, 15(1), 77-81. doi:10.1107/s0365110x62000158Adamová, G., Gardas, R. L., Nieuwenhuyzen, M., Puga, A. V., Rebelo, L. P. N., Robertson, A. J., & Seddon, K. R. (2012). Alkyltributylphosphonium chloride ionic liquids: synthesis, physicochemical properties and crystal structure. Dalton Transactions, 41(27), 8316. doi:10.1039/c1dt10466gGottlieb, H. E., Kotlyar, V., & Nudelman, A. (1997). NMR Chemical Shifts of Common Laboratory Solvents as Trace Impurities. The Journal of Organic Chemistry, 62(21), 7512-7515. doi:10.1021/jo971176vSheldrick, G. M. (2007). A short history ofSHELX. Acta Crystallographica Section A Foundations of Crystallography, 64(1), 112-122. doi:10.1107/s0108767307043930Allen, F. H., & Motherwell, W. D. S. (2002). Applications of the Cambridge Structural Database in organic chemistry and crystal chemistry. Acta Crystallographica Section B Structural Science, 58(3), 407-422. doi:10.1107/s0108768102004895Ramnial, T., Taylor, S. A., Bender, M. L., Gorodetsky, B., Lee, P. T. K., Dickie, D. A., … Clyburne, J. A. C. (2008). Carbon-Centered Strong Bases in Phosphonium Ionic Liquids. The Journal of Organic Chemistry, 73(3), 801-812. doi:10.1021/jo701289dDietzel, P. D. C., & Jansen, M. (2002). Tetramethylphosphonium hydrogen carbonate. Acta Crystallographica Section E Structure Reports Online, 58(9), o1003-o1004. doi:10.1107/s1600536802013168Li, H., Hou, Y., & Yang, Y. (2011). Tetraethylammonium bicarbonate trihydrate. Acta Crystallographica Section E Structure Reports Online, 67(8), o1991-o1991. doi:10.1107/s1600536811026080McMullan, R., & Jeffrey, G. A. (1959). Hydrates of the Tetran‐butyl and Tetrai‐amyl Quaternary Ammonium Salts. The Journal of Chemical Physics, 31(5), 1231-1234. doi:10.1063/1.1730574Smiglak, M., Hines, C. C., & Rogers, R. D. (2010). New hydrogen carbonate precursors for efficient and byproduct-free syntheses of ionic liquids based on 1,2,3-trimethylimidazolium and N,N-dimethylpyrrolidinium cores. 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Alkyltributylphosphonium chloride ionic liquids: synthesis, physicochemical properties and crystal structure. Dalton Transactions, 41(27), 8316. doi:10.1039/c1dt10466gM. B. Shiflett and A.Yokozeki, Phase Behaviour of Gases in Ionic Liquids, in Ionic Liquids UnCOILed: Critical Expert Overviews, ed. N. V. Plechkova and K. R. Seddon, Wiley, Hoboken, New Jersey, 2013, pp. 349–398Ibrahim, A. Y., Ashour, F. H., Ghallab, A. O., & Ali, M. (2014). Effects of piperazine on carbon dioxide removal from natural gas using aqueous methyl diethanol amine. Journal of Natural Gas Science and Engineering, 21, 894-899. doi:10.1016/j.jngse.2014.10.011Anonymous , Piperazine – Why It's Used And How It Works, The Contractor (Optimized Gas Treating, Inc.), Houston, 2008, 2 [4], http://www.ogtrt.com/files/contactors/vol_2_issue_4.pd

3-Methylpiperidinium ionic liquids

[EN] A wide range of room temperature ionic liquids based on the 3-methylpiperdinium cation core were produced from 3-methylpiperidine, which is a derivative of DYTEKs (R) A amine. First, reaction with 1-bromoalkanes or 1-bromoalkoxyalkanes generated the corresponding tertiary amines (Rm beta pip, R = alkyl or alkoxyalkyl); further quaternisation reactions with the appropriate methylating agents yielded the quaternary [Rmm(beta)pip]X salts (X-= I-, [CF3CO2]-or [OTf](-); Tf = -SO2CF3), and [Rmm(beta)pip][NTf2] were prepared by anion metathesis from the corresponding iodides. All [NTf2]-salts are liquids at room temperature. [Rmm(beta)pip]X (X-= I-, [CF3CO2]-or [OTf](-)) are low-melting solids when R = alkyl, but room temperature liquids upon introduction of ether functionalities on R. Neither of the 3-methylpiperdinium ionic liquids showed any signs of crystallisation, even well below 0 degrees C. Some related non-C-substituted piperidinium and pyrrolidinium analogues were prepared and studied for comparison. Crystal structures of 1-hexyl-1,3-dimethylpiperidinium tetraphenylborate, 1-butyl-3-methylpiperidinium bromide, 1-(2-methoxyethyl)1- methylpiperidinium chloride and 1-(2-methoxyethyl)-1-methylpyrrolidinium bromide are reported. Extensive structural and physical data are collected and compared to literature data, with special emphasis on the systematic study of the cation ring size and/or asymmetry effects on density, viscosity and ionic conductivity, allowing general trends to be outlined. Cyclic voltammetry shows that 3-methylpiperidinium ionic liquids, similarly to azepanium, piperidinium or pyrrolidinium counterparts, are extremely electrochemically stable; the portfolio of useful alternatives for safe and high-performing electrolytes is thus greatly extended.We would like to acknowledge the EPSRC NCS in Southampton for the single crystal X-ray diffraction data collection and INVISTA Intermediates for funding.Belhocine, T.; Forsyth, SA.; Gunaratne, HQN.; Nieuwenhuyzen, M.; Nockemann, P.; Vaca Puga, A.; Seddon, KR.... (2015). 3-Methylpiperidinium ionic liquids. Physical Chemistry Chemical Physics. 17(16):10398-10416. doi:10.1039/C4CP05936KS10398104161716C. Mikolajczak , M.Kahn, K.White and R. T.Long, Lithium-ion Batteries Hazard and Use Assessment, Springer, New York, 2012Choi, N.-S., Chen, Z., Freunberger, S. A., Ji, X., Sun, Y.-K., Amine, K., … Bruce, P. G. (2012). Challenges Facing Lithium Batteries and Electrical Double-Layer Capacitors. 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An improved method to measure the rate of vaporisation and thermal decomposition of high boiling organic and ionic liquids by thermogravimetrical analysis. Physical Chemistry Chemical Physics, 12(38

Production of H2 by Ethanol Photoreforming on Au/TiO2

A deposition-precipitation method is used to prepare Au/TiO 2 solids (0.45–1.7 wt% Au). These materials, consisting of gold nanoparticles (diameter range = 1.5–6.5 nm) supported on the surface of TiO 2 , are used as photocatalysts for the ethanol photoreforming reaction under either UV-rich or simulated solar light. The main products of such reactions are H 2 in the gas phase and acetaldehyde in the liquid phase according to the reaction CH 3 CH 2 OH → CH 3 CHO + H 2 . Among the gaseous products, H 2 amounts to around or above 99% in all cases; other minor products found in the gas phase are, in decreasing order of molar production: CH 4 > CO > C 2 H 4 > CO 2 > C 2 H 6 > C 3 H 8 . The photoactivity is lower under CO 2 atmosphere, as compared to analogous reactions performed under Ar. The H 2 production yields are very high (up to a maximum 30 mmol g cat−1 h −1 ) under UV irradiation, and increase with increasing gold loading. The reactions under simulated solar light also yield signifi cant amounts of H 2 (5–6 mmol g cat−1 h −1 ) as the main gaseous product.This work has been supported by the JAE-Doc program, co-funded by the Consejo Superior de Investigaciones Cientificas (CSIC) and the European Social Fund (ESF). A.V.P. is grateful to CSIC for a JAE-Doc post-doctoral grant. Financial support by the Generalitat Valenciana (Prometeo 20/2/014) is gratefully acknowledged.Vaca Puga, A.; Forneli Rubio, MA.; García Gómez, H.; Corma Canós, A. (2014). Production of H2 by Ethanol Photoreforming on Au/TiO2. Advanced Functional Materials. 24(2):241-248. doi:10.1002/adfm.201301907S24124824

Production of polyetheretherketone in ionic liquid media

[EN] Polyetheretherketones were successfully synthesised in an ionic liquid, namely 1-butyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}amide, by polycondensation reactions of hydroquinone with 4,4'-dihalobenzophenones in the presence of potassium carbonate at elevated temperatures (up to 320 degrees C). The materials thus produced were similar to polymers prepared in the solvent usually employed in commercial processes, i.e. diphenyl sulfone, as suggested by spectroscopic techniques and X-ray crystallography. By replacing volatile diphenyl sulfone with the effectively involatile ionic liquid, the separation efficiency was significantly improved but the molecular weights were lower.We acknowledge Dr S.R. Holding and T.S. Forsyth at Smithers Rapra Technology Limited for the gel permeation chromatographic analyses, and INVISTA Intermediates for funding.Gunaratne, HQN.; Langrick, CR.; Vaca Puga, A.; Seddon, KR.; Whiston, K. (2013). Production of polyetheretherketone in ionic liquid media. Green Chemistry. 15(5):1166-1172. doi:10.1039/C3GC36754AS1166117215

Conference report: Lake Constance turns green

Adamova, G.; Ferguson, J.; Ng, S.; Puga Vaca, A.; Rodriguez, H.; Rountree, S.; Seddon, K.... (2009). Conference report: Lake Constance turns green. Green Chemistry. 11(5):604-608. doi:10.1039/b822925mS60460811

New ionic liquids from azepane and 3-methylpiperidine exhibiting wide

New ionic liquids based on azepanium and 3-methylpiperidinium cations have been synthesised; they exhibit moderate viscosities and remarkably wide electrochemical windows, thereby showing promise, inter alia, as electrolytes and battery materials, and as synthetic media.Belhocine, T.; Forsyth, SA.; Gunaratne, HQN.; Nieuwenhuyzen, M.; Vaca Puga, A.; Seddon, KR.; Srinivasan, G.... (2011). New ionic liquids from azepane and 3-methylpiperidine exhibiting wide electrochemical windows. Green Chemistry. 13(1):59-63. doi:10.1039/c0gc00534gS5963131Wilkes, J. S., Levisky, J. A., Wilson, R. A., & Hussey, C. L. (1982). Dialkylimidazolium chloroaluminate melts: a new class of room-temperature ionic liquids for electrochemistry, spectroscopy and synthesis. Inorganic Chemistry, 21(3), 1263-1264. doi:10.1021/ic00133a078Wilkes, J. S. (2002). A short history of ionic liquids—from molten salts to neoteric solvents. Green Chemistry, 4(2), 73-80. doi:10.1039/b110838gHurley, F. H., & WIer, T. P. (1951). 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