- Structure, dynamics and morphology in the system M(CF3SO3)2 PEOn for M = Zn and Pb
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Ion pairing effects have been studied for M(CF3SO3)2 PEOn films with M = Zn and Pb, and n = 9, 16 and 24. Using FT-ir spectroscopy the SO3 and C-O-C stretching modes for CF3SO3s
- Wendsjoe, Aa.,Lindgren, J.,Paluszkiewicz, C.
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- Tetranuclear polypyridyl complexes of RuII and FeII: Synthesis, electrochemical, photophysical and photochemical behaviour
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Three heterotetranuclear complexes [{RuII(bpy) 2(LLn)}3FeII]8+ {bpy = 2,2′-bipyridine, n = 2, 4, 6; denoted [{Ru(LLn)} 3Fe]8+}, in which one iron centre is complexed by three RuII-tris-bipyridine-like moieties containing covalently bridging bis-bipyridine LLn ligands, have been synthesised and characterised. The stability and the electrochemical, photophysical and photochemical properties of these complexes have been investigated in CH3CN. The cyclic voltammograms of all complexes exhibit two successive reversible oxidation processes in the positive region, corresponding to the Fe II/FeIII and RuII/RuIII redox couples. These systems are clearly separated (ΔE1/2 about 300 mV), which indicates the absence of an electronic connection between the two subunits. In the negative region, three successive reversible four-electron systems are observed, corresponding to tho ligand-based reduction processes. The two oxidized forms of the complexes [{RuII(LLn)} 3FeIII]9+ and [{RuIII(LL n)}3FeIII]12+, which are obtained by two successive exhaustive electrolyses, are very stable. The [{Ru(LL n)}3Fe]8+ complexes are luminescent, which shows that the covalent linkage between the RuII-tris-bipyridine and FeII-tris-bipyridine subunits leads to an only partial quenching of the RuII* excited states by energy transfer to the Fe II centre. The luminescence lifetime and quantum yield are found to be independent of the complexes' concentration, thus indicating that the energy-transfer process is only due to an intramolecular electron-exchange mechanism. Quantitative photoinduced oxidation of the tetranuclear complexes has been performed by continuous photolysis experiments in the presence of a large excess of a diazonium salt, which plays the role of a sacrificial oxidant. Two successive oxidation processes (FeII → FeIII and RuII → RuIII) are observed. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.
- Lombard, Jean,Romain, Sophie,Dumas, Stephane,Chauvin, Jerome,Collomb, Marie-Noelle,Daveloose, Denis,Deronzier, Alain,Lepretre, Jean-Claude
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- Zn(OTf)2-mediated C[sbnd]H activation: An expeditious and solvent-free synthesis of aryl/alkyl substituted quinolines
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Zinc(II) triflate catalyzed three-component coupling reactions of alkynes, amines and aldehydes leading to the formation of aryl/alkyl substituted quinolines has been described. Notably, the reaction proceeded efficiently and effectively without the use of ligand, co-catalyst, solvent or inert atmosphere. This robust solvent-free process operates under an ambient atmosphere and avoids the use of precious metals, hazardous solvents and harsh reaction conditions. This atom economic process eliminates the waste generated in the multistep synthesis. Additionally, a pseudo three-component Povarov reaction of amines and butanal proceeds under the same green conditions enabling the formation of 2,3-dialkyl quinolines.
- Sarode, Prashant B.,Bahekar, Sandeep P.,Chandak, Hemant S.
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supporting information
p. 5753 - 5756
(2016/12/06)
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- Zn(OTf)2-Mediated Expeditious and Solvent-Free Synthesis of Propargylamines via C-H Activation of Phenylacetylene
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Zn(OTf)2-mediated expeditious and solvent-free synthesis of propargylamines via A3 coupling of aldehydes, amines, and phenylacetylene has been described. The described protocol proceeds effectively with variety of substituted benzaldehydes, enolizable aldehyde, and formaldehyde. Recyclability of the catalyst, low catalyst loading, and use of inexpensive catalyst are the key features of the present protocol.
- Sarode, Prashant B.,Bahekar, Sandeep P.,Chandak, Hemant S.
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supporting information
p. 2209 - 2212
(2016/10/12)
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- A method of manufacturing a metal salt aminoalkylsulfonic Perfluoropolyalkyl
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PROBLEM TO BE SOLVED: To provide a method for producing inexpensively and efficiently little-colored organic solvent solution of a metal salt of perfluoroalkyl sulfonic acid. SOLUTION: In this method for producing a metal salt of perfluoroalkyl sulfonic acid represented by general formula (1), a metal oxide is reacted with a perfluoroalkyl sulfonic acid in protonic polar organic solvent capable of dissolving the metal salt of the perfluoroalkyl sulfonic acid. [In the formula, M represents an atom selected from manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn) and rare-earth metals, m represents an integer from 0 to 9, and n represents an integer equal to the valence of M]. COPYRIGHT: (C)2013,JPO&INPIT
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Paragraph 0053
(2016/12/22)
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- Equilibrium and kinetics of the dinuclear complex formation between N,N′-ethylenebis(salicylideneiminato)copper(II) and metal(II,I) ions in acetonitrile
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The equilibrium constants and rate constants of the reactions between N,N′-ethylenebis(salicylideneiminato)copper(II) ([Cu(salen)]) and metal(II,I) ions in acetonitrile have been spectrophotometrically determined. [Cu(salen)] acts as a didentate ligand to form a dinuclear complex. The rate constants for the very labile Mn(II), Fe(II), and Zn(II) ions were directly evaluated using a variable flow-rate instrument that was newly constructed for this study. The rate constants of the dinuclear complex formation for a series of metal(II) ions vary in parallel with those of the acetonitrile solvent exchange on the corresponding metal(II) ions. This finding indicates that the dinuclear complex formation reaction of the metal(II) ions proceeds via almost the same reaction mechanism as for the acetonitrile solvent exchange reaction.
- Inada, Yasuhiro,Mochizuki, Koji,Tsuchiya, Takashi,Tsuji, Hiroaki,Funahashi, Shigenobu
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p. 3009 - 3014
(2008/10/09)
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- Synthesis, and crystal and molecular structures of the triflato and trifluoroacetato complexes of zinc, Zn(O3SCF3)2(DME)2 and [Zn(O2CCF3)2(DME)]n
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Anhydrous Zn(O3SCF3)2 and Zn(O2CCX3)2, X=F, Cl, Br were obtained in substantially quantitative yields from ZnO (or ZnEt2 in the case of the bromide derivative) and a mixture of the corresponding acid and anhydride in heptane as medium. The reactions are rapid and moderately exothermic. Recrystallization of the triflate and trifluoroacetate complexes from dimethoxyethane (DME) produced single crystals of Zn(O3SCF3)2(DME)2 (1) and [Zn(O2CCF3)2(DME)]n (2) suitable for X-ray diffraction studies. In both compounds zinc is hexacoordinated with a pseudo-octahedral geometry. Compound 1 is constituted by mononuclear molecules with terminal monodentate O3SCF3 ligands in trans position. A polynuclear chain structure was found for 2 with zinc atoms joined alternatively by triple and single carboxylato bridges, and with bidentate terminal DME.
- Dell'Amico, Daniela Belli,Boschi, Daniele,Calderazzo, Fausto,Labella, Luca,Marchetti, Fabio
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p. 149 - 154
(2008/10/08)
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- Solvation structures of manganese(II), iron(II), cobalt(II), nickel(II), copper(II), zinc(II), and gallium(III) ions in methanol, ethanol, dimethyl sulfoxide, and trimethyl phosphate as studied by EXAFS and electronic spectroscopies
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Solvation structures of the Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), and Ga(III) ions in methanol (MeOH), ethanol (EtOH), dimethyl sulfoxide (DMSO), and trimethyl phosphate (TMP) have been determined using extended X-ray absorption fine structure (EXAFS) spectroscopy. In MeOH, EtOH, and DMSO, the solvation structures of all metal(II,III), ions are 6-coordinate octahedral as in water, and the M-O bond lengths are similar to those in water. In the bulky solvent TMP, the 5-coordinate solvation structure is observed for the Zn(II) ion without ligand-field stabilization. The Ga(III) ion has the 6-coordinate solvation structure in TMP despite its smaller ionic radius than the Zn(II) ion because of the higher charge density on the Ga(III) ion. In the cases of the Mn(II), Fe(II), Co(II), Ni(II), and Cu(II) ions, the electronic absorption spectra have been measured in MeOH, EtOH, and DMSO. All solutions for each metal(II) ion show a spectral pattern similar to that in water, which is consistent with the results of the EXAFS measurements.
- Inada,Hayashi,Sugimoto,Funahashi
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p. 1401 - 1406
(2007/10/03)
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- Compositions of retinoids substituted with a dithiane ring, their use, and process for preparing the compounds
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The invention relates to a stereospecific derivative of formula: STR1 in which R is hydrogen or a C 1 -C 4 thioalkyl. The invention also relates to the use of these compounds for the manufacture of stereospecific retinal or retinoic acid, as well as to a process for preparing the retinoids of formula (I). The invention finally relates to a cosmetic or pharmaceutcial composition which contains at least one compound of formula (I) in a suitable vehicle; the pharmaceutical composition according to the invention may be used for treating dermatological, rheumatic, respiratory or ophthalmological conditions.
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- Propenals substituted with a dithiane ring and processes for the preparation of these propenals
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Propenals of formula: STR1 in which formula R is H or a C1 -C4 thioalkyl radical, the dithiane ring being at the cis position in relation to the aldehyde function when R is H and at the trans position when R is a thioalkyl radical. The invention also relates to two processes for the preparation of these propenals.
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- Process for the preparation of addition products of epoxides and hydroxylated compounds
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Process for the preparation of addition products of epoxides and hydroxylated compounds, characterized by the fact that it comprises the reaction of an epoxide and a hydroxylated compound in the homogeneous liquid phase, in the presence, as catalyst, of a salt of trifluoromethanesulphonic acid.
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