429-06-1Relevant articles and documents
Electrochemistry as an attractive and effective tool for the synthesis and immobilization of porphyrins on an electrode surface
Hebié, Seydou,Dimé, Abdou K. D.,Devillers, Charles H.,Lucas, Dominique
, p. 8281 - 8289 (2015)
Magnesium(II) 10-phenyl-5,15-p-ditolylporphyrin is easily and cleanly transformed by electrolysis. A nitro group is first introduced at the free meso position by anodic substitution. Hydrogenation into the amine is then carried out electrocatalytically under ambient conditions with water as a hydrogen supplier. The synthesized porphyrin under the nickel(II) form can be covalently grafted onto a platinum electrode by electrochemical reduction of the diazonium cation, generated in situ by a reaction of the nickel(II) aminoporphyrin with sodium nitrite and trifluoroacetic acid. The electrosynthesized thin film gives an electrochemical response typical of a porphyrin material. Films grown under our conditions have a maximum surface coverage of approximately 5×10-10 mol cm-2. The modified electrode exhibits a reproducible electrochemical behavior and a good level of stability over potential cycling and exposition to air. Being choosy: Selective approaches based on electrochemistry have been developed to yield different porphyrins. The final synthesized porphyrin is covalently attached to the electrode surface through the electroreduction of the corresponding diazonium generated in situ in organic media (see figure; RE, CE, WE=ref, counter and working electrode, respectively). The results demonstrate that electrochemistry is an efficient alternative tool for the synthesis of designed porphyrins and their use in surface modification.
Towards sustainable synthesis of pyren-1-yl azoliums via electrochemical oxidative C-N coupling
De Robillard, Guillaume,Makni, Oumayma,Cattey, Hélène,Andrieu, Jacques,Devillers, Charles H.
, p. 4669 - 4679 (2015)
Electrosynthesis of 1-methyl-3-(pyren-1-yl)-1H-imidazol-3-ium tetrafluoroborate via oxidative C-N coupling of pyrene with methylimidazole is optimized with the aim to reduce waste and simplify the experimental setup. Several parameters are tested such as cell configuration (number of compartments), pyrene concentration, amount of nucleophile, electrosynthetic method (potentiostatic/galvanostatic), amount of electrons, atmosphere (Ar/air), solvent quality and presence/absence of a supporting electrolyte. The optimized conditions are successfully applied to the synthesis of 1-methyl-3-(pyren-1-yl)-1H-benzimidazol-3-ium tetrafluoroborate, 1-methyl-4-(pyren-1-yl)-1H-1,2,4-triazol-4-ium tetrafluoroborate and 3-(pyren-1-yl)-benzothiazol-3-ium tetrafluoroborate. These four pyren-1yl-azolium salts are characterized by NMR, MS, elemental analysis, UV-Vis absorption and emission spectroscopy. The X-ray crystallographic structures of 1-methyl-3-(pyren-1-yl)-1H-imidazol-3-ium tetrafluoroborate and 1-methyl-3-(pyren-1-yl)-1H-benzimidazol-3-ium tetrafluoroborate are presented.
The influence of temperature and concentration on viscous flow of solutions of Et4NBF4 in propylene carbonate
Afanas'ev,Tyunina, E. Yu.,Chekunova
, p. 2069 - 2073 (2009)
Solutions of tetraethylammonium tetrafluoroborate in propylene carbonate were studied by viscometry and densimetry over the concentration range 0.08-1 mol/kg at 283.15, 298.15, and 308.15 K. The concentration dependence of the viscosity of solutions was described by the Angell and Bachinskii equations. The thermodynamic parameters of activation of viscous flow of solutions of Et 4NBF4 in propylene carbonate were estimated using the approach suggested by Eyring and Andrade. The solvation of tetraethylammonium tetrafluoroborate in propylene carbonate was found to be insignificant. The activation energy of viscous flow in solutions remained constant over the temperature range studied. Viscous flow was largely determined by solvent destructuring as the concentration of the electrolyte and temperature increased.
Electrophilic additions of metal fragments containing 11- and 12-group elements to the anion carbide cluster [Fe5MoC(CO)17]2-. X-ray crystal structures of (NEt4)[Fe5MoAuC(CO)17(PMe3)] and [Fe5MoAu2C(CO)17(dppm)]
Reina, Roser,Rodríguez, Laura,Rossell, Oriol,Seco, Miquel,Font-Bardia, Mercè,Solans, Xavier
, p. 1575 - 1579 (2001)
The reaction of (NEt4)2[Fe5MoC(CO)17] with cationic metal fragments gives a series of clusters whose most striking structural feature is the selective addition of the incoming metal units on the triangular Fe2Mo face of the starting anion. The use of Au2(dppm)2+ (dppm = diphenylphosphinomethane) gives the cluster [Fe5MoAu2C(CO)17(dppm)] in which the di-gold fragment adopts an unprecedented bonding mode.
A four-ethyl four simple method for preparing ammonium borofluoride (by machine translation)
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Paragraph 0021-0042; 0045-0052, (2018/10/11)
The invention discloses an electronic power supply for electrolytic salt — four four ethyl ammonium fluoroborate preparation method, by adopting commercial four-ethyl ammonium chloride tetrafluoride and sodium as a synthetic raw material, water as a solvent, in accordance with the four-ethyl ammonium chloride: beryllium sodium=0.2 - 1:1 molar ratio of feeding, after stirring and reacting collecting solid, obtained four four ethyl [...] fluoborate; the resulting crude product at room temperature for a small quantity of water dispersion is vigorously agitated for 10 - 60 minutes, filter; then the solid for physical and - 10 °C - 0 °C ethanol washing, after drying, four by four ethyl ammonium fluoborate. The invention feeding directly after the crude product can be filtered to obtain products, by the one-step simple purification can get high sterling, simple steps, the production cycle is short, high yield, high purity, in the whole process of the used organic solvent is only a small amount of washing with ethanol, does not pollute the environment, the requirements on equipment is extremely low, in the process of synthesis without the vacuum, anti-corrosion, heating, energy consumption and cost are significantly reduced. (by machine translation)
A Ni(III) complex stabilized by silica nanoparticles as an efficient nanoheterogeneous catalyst for oxidative C-H fluoroalkylation
Khrizanforov, Mikhail N.,Fedorenko, Svetlana V.,Strekalova, Sofia O.,Kholin, Kirill V.,Mustafina, Asiya R.,Zhilkin, Mikhail Ye.,Khrizanforova, Vera V.,Osin, Yuri N.,Salnikov, Vadim V.,Gryaznova, Tatyana V.,Budnikova, Yulia H.
supporting information, p. 11976 - 11982 (2016/08/05)
We have developed NiIII-doped silica nanoparticles ([(bpy)xNiIII]@SiO2) as a recyclable, low-leaching, and efficient oxidative functionalization nanocatalyst for aromatic C-H bonds. The catalyst is obtained by doping the complex [(bpy)3NiII] on silica nanoparticles along with its subsequent electrooxidation to [(bpy)xNiIII] without an additional oxidant. The coupling reaction of arenes with perfluoroheptanoic acid occurs with 100% conversion of reactants in a single step at room temperature under nanoheterogeneous conditions. The catalyst content is only 1% with respect to the substrates under electrochemical regeneration conditions. The catalyst can be easily separated from the reaction mixture and reused a minimum of five times. The results emphasize immobilization on the silica support and the electrochemical regeneration of NiIII complexes as a facile route for developing an efficient nanocatalyst for oxidative functionalization.
