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.
Synthesis and characterization of {Ni(NO)}10 and {Co(NO) 2}10 complexes supported by thiolate ligands
Tennyson, Andrew G.,Dhar, Shanta,Lippard, Stephen J.
, p. 15087 - 15098 (2008)
Nitric oxide is an important molecule in biology and modulates a variety of physiological and pathophysiological processes. Some of its regulatory functions are exerted through interactions with redox-active elements, including iron, nickel, cobalt, and sulfur. Metalloenzymes containing [nFe-nS] (n = 2 or 4) clusters can be activated or inactivated by reaction with NO, affording dinitrosyl iron complexes. Studies of the NO chemistry of small-molecule iron thiolate complexes have provided insight into these biological processes and suggested probable intermediates. To explore this chemistry from a different perspective, we prepared nickel and cobalt thiolate complexes and investigated their reactions with NO and related compounds. We report here the first examples of anionic complexes containing {Ni(NO)}10 and {Co(NO) 2}10 units, the reactivity of which suggests possible intermediates in the interconversion of iron thiolate nitrosyl compounds. Our results demonstrate new chemistry involving NO and simple complexes of nickel and cobalt supported by thiolates, which have been known for more than 30 years. The use of mass balance methodology was key to their discovery. Among the novel complexes reported are (Et4N)2[Ni(NO)(SPh)3] (2), from (Et4N)2[Ni(SPh)4] (1) and NO, (Et4N)2[Ni2(NO)2(μ-SPh) 2(SPh)2] (3), from 1 and NO+ or 2 and Me 3O+, (Et4N)[Co(NO)2(SPh) 2] (5), from (Et4N)2[Co(SPh)4] (4) and NO, and [Co3(NO)6(μ-SPh)3] (6), from 5 and Me3O+. In the syntheses of 2 and 5, NO could be replaced by the convenient solid Ph3CSNO.
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.
Electrochemical phosphorylation of coumarins catalyzed by transition metal complexes (Ni—Mn, Co—Mn)
Strekalova,Khrizanforov,Gryaznova,Khrizanforova,Budnikova, Yu. H.
, p. 1295 - 1298 (2016)
A possibility of electrochemical phosphorylation of coumarins (coumarin, 6-methylcoumarin, 7-methylcoumarin) with diethyl phosphite was shown. The approach is based on the oxidation of a mixture of the aromatic compound and diethyl phosphite (1: 1) under mild conditions (room temperature, atmospheric pressure) in the presence of a bimetallic catalytic systems: MnIIbipy/NiIIbipy and MnIIbipy/CoIIbipy (bipy is the 2,2′-bipyridine). This method allows one to obtain diethyl arylphosphonates in high yields (up to 70%) and 100% conversion of the phosphite.
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.
Mechanism of the Platinum(II)-Catalyzed Hydroamination of 4-Pentenylamines
Bender, Christopher F.,Brown, Timothy J.,Widenhoefer, Ross A.
, p. 113 - 125 (2016)
The mechanism of the platinum(II)-catalyzed intramolecular hydroamination of benzyl 4-pentenylamines has been evaluated under stoichiometric and catalytic conditions. Reaction of a benzyl 2,2-disubstituted 4-pentenylamine with [(PPh3)Pt(μ-Cl)Cl]2 forms a thermally sensitive platinum amine complex that undergoes irreversible, intramolecular ligand exchange with the pendant C=C bond to form a reactive platinum π-alkene complex. The π-alkene complex undergoes rapid, outer-sphere C-N bond formation, evidenced by the anti addition of Pt and N across the complexed C=C bond, to form a thermally stable zwitterionic platinamethylpyrrolidinium complex. The zwitterionic complex is rapidly and exergonically deprotonated by free amine to form a neutral, bicyclic azaplatinacyclobutane complex that likely exists as a discrete 1:1 adduct with ammonium salt in the nonpolar reaction medium and that represents the resting state of the catalytic cycle. Turnover-limiting intramolecular protodemetalation of the azaplatinacyclobutane-ammonium adduct followed by ligand exchange releases the 2-methylpyrrolidine product.
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.
Fe and Ni-catalyzed electrochemical perfluoroalkylation of C—H bonds of coumarins
Khrizanforov,Strekalova,Grinenko,Khrizanforova,Gryaznova,Budnikova, Yu. H.
, p. 1446 - 1449 (2017)
A new method for the preparation of perfluoroalkylcoumarins in a single step is developed. The compounds are prepared via electrocatalytic reduction of a 1 : 1 mixture of an aromatic compound (coumarin, 6-methylcoumarin, and 7-methylcoumarin) and a fluoroalkylating reagent under mild conditions (room temperature, normal pressure) using [bipyFeII] or [bipyNiII] complexes as catalysts. The developed method makes it possible to obtain perfluoroalkylcoumarins in high yields and 100% conversion of the fluoroalkylating reagent.
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 general diastereoselective synthesis of highly functionalized ferrocenyl ambiphiles enabled on a large scale by electrochemical purification
Lerayer, Emmanuel,Renaut, Patrice,Roger, Julien,Pirio, Nadine,Cattey, Hélène,Devillers, Charles H.,Lucas, Dominique,Hierso, Jean-Cyrille
supporting information, p. 6017 - 6020 (2017/07/11)
A general synthesis of highly functionalized ferrocenes, which include (P,B)- and (N,B)-ambiphiles, has been developed at a multigram scale. Diastereoselective stepwise modification of di-tert-butylated ferrocenes included the unprecedented separation of electroactive species. Bulky alkyl groups on ferrocenes ensure planar chirality of ambiphiles and enforce closer proximity of antagonist Lewis functions.
