- 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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- Formation and Deprotonation Kinetics of the Sitting-Atop Complex of Copper(II) Ion with 5,10,15,20-Tetraphenylporphyrin Relevant to the Porphyrin Metalation Mechanism. Structure of Copper(II)-Pyridine Complexes in Acetonitrile As Determined by EXAFS Spectroscopy
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The formation of a sitting-atop (SAT) complex of Cu(II) ion with 5,10,15,20-tetraphenylporphyrin (H2tpp) in acetonitrile has been observed, and the kinetic parameters for the formation were determined as follows; kso = (3.6 ±0.1) × 105 mol-1dm3 at 25.0 °C, ΔHso? = 56 ±5 kJ mol-1, and ΔSSO? = 46 ±19 J mol-1 K-1. The 1H NMR spectrum of the SAT complex (Cu(H2tpp)2+) indicated that two pyrrolenine nitrogens coordinate to the Cu(II) ion and that two protons bound to the pyrrole nitrogens remain. The protons were abstracted by the addition of pyridine (py) as the Br?nsted base to give the Cu(tpp) metalloporphyrin. In the presence of py, the product for the reaction of the Cu(II) ion with H2tpp was Cu(tpp) instead of the SAT complex. The observed conditional rates for the formation of Cu(H2tpp)2+ and Cu(tpp) were interpreted by the contribution of Cu2+, Cu(py)2+, and Cu(py)22+ species, and the second-order rate constants of the SAT complex formation were kS1 = (3.5 ± 0.3) × 104 mo-1 dm3 s-1 for Cu(py)2+ and kS2 = 90 ± 2 mol-1 dm3 s-1 for Cu(py)22+. Deprotonation rates were measured by following the reaction between the SAT complex and py as a function of the py concentration, and the second-order rate constant was determined to be (2.3 ± 0.1) × 102 mol-1 dm3 s-1. The present kinetic results have indicated that the SAT complex exists during the course of the metalation process and that the SAT complex formation is a rate-determining step.
- Inada, Yasuhiro,Sugimoto, Yumi,Nakano, Yuko,Itoh, Yuki,Funahashi, Shigenobu
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- Copper-63 NMR line width study of the copper(I)-acetonitrile system
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The principal focus of this study is the 63Cu NMR line widths in Cu(I)-acetonitrile (AN) solutions. The variations with the concentrations of Cu(I) salts (trifluoromethanesulfonate and perchlorate), added salts, water, chloride ion, and temperature have been studied. A quantitative analysis shows that the anomalous temperature dependence of the line widths is not due to ion pairing or anion complexation but results primarily from formation of a species with a different coordination number or less symmetrical arrangement of AN ligands than in the normal tetrahedral Cu(AN)4+ ion. Solvent viscosity and ion pairing (with triflate) also are identified as factors having the expected effects on the line widths. The results of earlier studies also are discussed and analyzed by the current model where possible.
- Irangu, Japhet K.,Jordan
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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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- Reaction of copper(II) with ferrocene and 1,1′-dimethylferrocene in aqueoys acetonitrile: The copper(II/I) self-exchange rate
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The kinetics of the reactions of copper(II) with ferrocene (Fc) and 1,1′-dimethylferrocene (Dmfc) have been studied at 25°C in aqueous acetonitrile (AN) containing 50-97.5 vol % AN. With increasing % AN, the rate constant increases along with the driving-force for the reaction. The results are analyzed in terms of Marcus theory to estimate the Cu(II/I) electron self-exchange rate constant (K11) for the system. Over the solvent range studied, the calculated k11 changes from 1.1 × 10 -9 to 17 × 10-9 M-1 s-1, with an average value of 5 × 10-9. In addition, the structures of the trifluoromethanesulfonate salts of [Cu(AN)4]+, [Cu(OH2)2(AN)2]2+, and [Cu(AN) 4]2+ are reported. It is found that the Cu-NCCH 3 bond-length difference between the Cu(I) and Cu(II) oxidation states is only ～0.02 A.
- Irangu, Japhet,Ferguson, Michael J.,Jordan, Robert B.
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- On the quenching of MLCTRe-bpy luminescence by Cu(II) species in Re(I) polymer micelles
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Transmission electron microscopy (TEM) and dynamic light scattering (DLS) studies on acetonitrile solutions of the polymer {[(vpy)2-vpyRe(CO) 3bpy] CF3SO3}200 demonstrated that the Re(I) polymer molecules aggregate to form spherical micelles of radius R = 156 nm. Coordination of Cu(II) species to the Re (I) polymer causes a decrease in the micelle radius and a distortion from the spherical shape. Besides, the coordination of Cu(II) species to the {[(vpy)2-vpyRe(CO) 3bpy] CF3SO3}200 polymer produces the quenching of the metal to ligand charge transfer (MLCT) excited state by energy transfer processes that are more efficient than those in the quenching of the monomer pyRe(CO)3bpy+ luminescence by Cu(II). Moreover, the kinetics of the quenching by Cu(II) do not follow a Stern-Volmer behavior. Conversely, the quenching of the MLCT luminescence of the Re(I) polymer by the sacrificial electron donor 2,2′,2″-nitrilotriethanol, TEOA, follows a Stern-Volmer kinetics. A comparison is made between the quenching by CuX2 (X = Cl or CF3SO3) and TEOA.
- Wolcan, Ezequiel,Alessandrini, Jose L.,Feliz, Mario R.
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- EXAFS Study on the Coordination Chemistry of the Solvated Copper(II) Ion in a Series of Oxygen Donor Solvents
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The structures of the solvated copper(II) ion in water and nine organic oxygen donor solvents with similar electron-pair donor ability, but with different space-demanding properties at coordination, have been studied by EXAFS. N,N′-Dimethylpropyleneurea and N,N,N′,N′-tetramethylurea are sufficiently space demanding at coordination to make the axial positions not accessible, resulting in square-planar copper(II) solvate complexes with an intense green color. The mean Cu-O bond distances in these two solvate complexes are 1.939(3) and 1.935(3) ?, respectively. The best fits of the remaining solvates, which are light blue in different hues, are obtained with a Jahn-Teller distorted-octahedral model consisting of four strongly bound solvent molecules in the equatorial positions at 1.96(2) ? and two in the axial positions but with different Cu-Oax bond distances: ca. 2.15 and 2.32 ?. This is in agreement with observations in solid-state structures of compounds containing hexaaquacopper(II) complexes crystallizing in noncentrosymmetric space groups and all reported crystal structures containing a [Cu(H2O)5(O-ligand)] complex with Jahn-Teller distortion. Such a structure is in agreement with previous EPR and EXAFS studies proving the hydrated copper(II) ion to be a noncentrosymmetric complex in aqueous solution. The refinements of the EXAFS data of the solids [Cu(H2O)6](ClO4)2, [Cu(H2O)6](BrO3)2, [Cu(H2O)6]SiF6, Cu(NO3)2·2.5H2O, and CuSO4·5H2O gave Cu-O bond distances significantly different from those reported in the crystallographic studies but similar to the configuration and bond distances in the hydrated copper(II) ion in aqueous solution. This may depend on whether the orientation of the axial positions is random in one or three dimensions, giving a mean structure of the solid with symmetry higher than that of the individual complexes. This study presents the very first experimental data from the new X-ray absorption spectroscopy beamline Balder at the MAX IV synchrotron radiation facility in Lund, Sweden, as well as the utilized properties of the beamline.
- Bajnóczi, éva G.,Just, Justus,Klementiev, Konstantin,Lundberg, Daniel,Persson, Ingmar,Sigfridsson Clauss, Kajsa G. V.
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- Training a Constitutional Dynamic Network for Effector Recognition: Storage, Recall, and Erasing of Information
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Constitutional dynamic libraries (CDLs) of hydrazones, acylhydrazones, and imines undergo reorganization and adaptation in response to chemical effectors (herein metal cations) via component exchange and selection. Such CDLs can be subjected to training by exposition to given effectors and keep memory of the information stored by interaction with a specific metal ion. The long-term storage of the acquired information into the set of constituents of the system allows for fast recognition on subsequent contacts with the same effector(s). Dynamic networks of constituents were designed to adapt orthogonally to different metal cations by up- and down-regulation of specific constituents in the final distribution. The memory may be erased by component exchange between the constituents so as to regenerate the initial (statistical) distribution. The libraries described represent constitutional dynamic systems capable of acting as information storage molecular devices, in which the presence of components linked by reversible covalent bonds in slow exchange and bearing adequate coordination sites allows for the adaptation to different metal ions by constitutional variation. The system thus performs information storage, recall, and erase processes.
- Holub, Jan,Vantomme, Ghislaine,Lehn, Jean-Marie
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supporting information
p. 11783 - 11791
(2016/10/07)
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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 0055
(2016/12/22)
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- Copper mediated stereoselective synthesis of C-glycosides from unactivated alkynes
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A highly stereoselective rapid C-glycosylation reaction has been developed between glycal and unactivated alkynes in the presence of coppertriflate and ascorbic acid at low catalyst loading and at room temperature. A wide variety of glycals and aryl acetylenes participate in the reaction smoothly. TfOH generated during the reduction of Cu(OTf)2 by ascorbic acid may be the active catalyst for the glycosylation. The Royal Society of Chemistry 2013.
- Kusunuru, Anil Kumar,Tatina, Madhubabu,Yousuf, Syed Khalid,Mukherjee, Debaraj
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supporting information
p. 10154 - 10156
(2013/10/22)
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- Copper(I)-catalyzed hydrophosphination of styrenes
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Hydrophosphination of styrenes has been accomplished with metal salts for the first time. (CuOTf)2·toluene complex is the catalyst of choice, but CuCl can also be used. "In-situ" EPR and NMR studies suggest Cu(I) as the catalytically active metal species, giving exclusively the anti-Markovnikov product. Phosphine oxides or β-ketophosphine oxides can be prepared in one-pot by oxidation with molecular oxygen.
- Leyva-Pérez, Antonio,Vidal-Moya, Jose A.,Cabrero-Antonino, Jose R.,Al-Deyab, Salem S.,Al-Resayes, Saud I.,Corma, Avelino
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p. 362 - 367
(2011/02/17)
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- Stereoselective cyclopropanation of serine- and threonine-derived oxazines to access new morpholine-based scaffolds
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A general strategy for the synthesis of novel, orthogonally protected scaffolds based on the unique 2-oxa-5-azabicyclo[4.1.0]heptane structure is presented. The described reaction sequence takes advantage of easily available starting materials such as serine and threonine and leads to stereochemically dense structures in few, high-yielding synthetic steps. We show how the stereochemistry can be easily tuned by starting from different β-hydroxy-α-amino acids and also by means of a transition metal-catalyzed cyclopropanation step. The compounds find application as constrained templates for the construction of geometrically diversified libraries of compounds.
- Sladojevich, Filippo,Trabocchi, Andrea,Guarna, Antonio
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p. 3328 - 3336
(2009/02/05)
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- Novel succinate derivative compounds useful as cysteine protease inhibitors
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Disclosed are novel succinate derivative compounds of the formula (I)/(Ia): wherein R1, R2, R3, R4, R5, R6, R7, X and A are defined herein. The compounds are useful as inhibitors of cysteine proteases. Also disclosed are methods of using and methods of making such compounds.
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- Succinate derivative compounds useful as cysteine protease inhibitors
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Disclosed are novel succinate derivative compounds of the formula(I)/(Ia): wherein R1, R2, R3, R4, R5, R6, R7, X and A are defined herein. The compounds are useful as inhibitors of cysteine proteases. Also disclosed are methods of using and methods of making such compounds.
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- Electrochemistry, Stability, and Alkene Complexation Chemistry of Copper(I) Triflate in Aqueous Solution. Potential for Use in Electrochemically Modulated Complexation-Based Separation Processes
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Copper(I) trifluoromethanesulfonate (CuOTf), which is insoluble in water, reacted with vinyl sulfonate anion (VS) to form a water soluble complex (concentrations > 0.1 M). Acidic CuOTf solutions prepared with relatively large VS/Cu(I) ratios were comparable in stability to solutions containing excess chloride ion. Reversible binding of alkenes (ethylene, 1,3-butadiene and 1-butene) to copper(I) in aqueous CuOTf/VS solutions was observed by 1H-NMR. The copper(I) displayed a competitive reaction with VS and the alkenes. This allowed the binding affinity of the alkenes to the copper(I) to be calculated based on the proton chemical shift for VS. The strength of alkene complexation followed the order ethylene > 1-butene ≈ 1,3-butadiene. The electrochemistry for the Cu(II/I) couple showed a quasi-reversible reaction that depended on acidity and the concentration of VS in the solution. Binding to copper(I) caused substantial amounts of the alkenes to be absorbed into CuOTf/VS solutions from the gas phase, especially at low [VS]/[Cu(I)] ratios. Calculations indicated that CuOTf in aqueous solution containing VS is superior to CuCl in chloride media for electrochemically modulated complexation-based separation of alkenes from alkanes.
- Suzuki, Takayuki,Noble, Richard D.,Koval, Carl A.
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p. 136 - 140
(2008/10/09)
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- Stability of Cu+ and Cu2+ complexes with cryptands in aprotic media
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The effect of solvent on the stability constants of copper (I) and (II) complexes with macrocyclic and macrobicyclic ligands: 23, 22, 21, 211, 221, 222, 222B and 222BB, were investigated by potentiometric titration in acetonitrile, propanenitrile, butanenitrile, benzonitrile, acetone, propylene carbonate, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide and in tetramethylene sulfone (sulfolane). In all cases 1:1 complexes were detected. The stabilities depend upon the solvent, ligand and oxidation state of the copper cation. The strong solvation of the Cu+ cation in nitriles leads to CuL+ complexes whose stabilities are within the range of 1.5+ and CuL2+ complexes lie within a similar range. In all cases the presence of the macrocycle increases the stability of the monovalent oxidation state even if the divalent cation forms a more stable complex. In the remaining solvents the monovalent copper form is unstable, but the stabilities of the divalent copper complexes, CuL2+, expressed as log K, range from 1.5 up to 25. CNRS-Gauthier-Villars.
- Lewandowski, Andrzej,Malinska, Jadwiga
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p. 653 - 657
(2008/10/08)
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- An EXAFS spectroscopic study of solvates of copper(I) and copper(II) in acetonitrile, dimethyl sulfoxide, pyridine, and tetrahydrothiophene solutions and a large-angle X-ray scattering study of the copper(II) acetonitrile solvate in solution
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X-ray absorption edge and EXAFS spectra of the acetonitrile, dimethyl sulfoxide, pyridine and tetrahydrothiophene solvated copper(I) ions and the acetonitrile and dimethyl sulfoxide solvated copper(II) ions have been measured in solution. Analysis reveals that the copper(I) solvates are most probably tetrahedral, and the following Cu-solvate bond distances have been found: Cu-N = 1.99(2) ? in acetonitrile, Cu-O = 2.09(4) ? in dimethyl sulfoxide, Cu-N = 2.06(1) ? in pyridine, and Cu-S = 2.30(1) ? in tetrahydrothiophene. The copper(II) solvates are most probably Jahn-Teller distorted octahedrons, and the following equatorial Cu-solvate bond distances have been found: Cu-N = 1.99(1) ? in acetonitrile, and Cu-O = 1.98(1) ? in dimethyl sulfoxide. An 1.0 M solution of copper(II) trifluoromethanesulfonate in acetonitrile has been studied by means of the large-angle X-ray scattering technique, and the following Cu-N and Cu-C distances have been found for the Cu(CH3CN)42+ complex: 1.99(1) and 3.12(1) ?, respectively. No solvate molecules in the axial positions could however be seen by any of the techniques used. The structure of the tetraaquacopper(I) ion has been assumed to be tetrahedral, and from a correlation between the difference in bond length between the copper(I) and copper(II) solvates and the disproportionation constants of copper(I) in the solvent, the Cu-O bond distance is predicted to be approximately 0.14 ? longer than the equatorial Cu-O distances in the Jahn-Teller distorted hexaaquacopper(II) complex, thus about 2.13 ?.
- Persson, Ingmar,Penner-Hahn, James E.,Hodgson, Keith O.
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p. 2497 - 2501
(2008/10/08)
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- Effect of noncomplexing anions on copper(II)-macrocyclic tetrathiaether complexes. Evaluation of dissociation kinetics in aqueous solution using mercury(II) ion as scavenger
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As a follow-up to earlier work which indicated that copper(II)-macrocyclic tetrathiaether complexes are stabilized by the presence of anions normally considered to be noncomplexing, the dissociation kinetics of Cu(II) complexes with [12]aneS4, [13]aneS4, and [14]aneS4 have been investigated in aqueous solution at 25°C as a function of perchlorate ion concentration using aquamercury(II) ion as the scavenging species. For the CuII([14]aneS4) complex, additional kinetic studies have been conducted in the presence of tetrafluoroborate, trifluoromethanesulfonate, and nitrate ions. For all systems, the kinetic data are interpreted to represent a combination of the direct CuIIL complex dissociation pathway plus a parallel pathway in which the Hg(II) actively displaces the Cu(II) from the ligand, presumably by forming coordinate bonds to the ligand before CuIIL is fully dissociated. Both the direct CuIIL dissociation rate and the Hg(II) displacement rate decrease markedly upon increasing the concentration of the perchlorate, tetrafluoroborate, and trifluoromethanesulfonate ions but show no dependence upon nitrate ion. For the studies involving variable perchlorate ion concentration, two specific dissociation rate constants (kCuL and kCuLX) are resolved representing the dissociation of CuL2+ and the anion adduct CuLX+ (where X- represents ClO4-); in addition, two specific mercury(II) displacement rate constants (kHgCuL′ and kHgCuLX′, both expressed as first-order rate constants after correction for outer-sphere complex formation) are resolved for these same two Cu(II) complex species. The resultant values at 25°C for all four specific rate constants (s-1), listed in the order KCuL, kCuLX, kHgCuL′, and kHgCuLX′, are as follows: CuII([12]aneS4), 8 ± 2, 1.3 ± 0.4, (2.6 ± 0.3) × 103, (9 ± 6) × 101; CuII([13]aneS4), 95 ± 11, 9 ± 2, (1.0 ± 0.1) × 104, (4 ± 1) × 103; CuII([14]aneS4), 18 ± 2, 1.2 ± 0.3, (1.4 ± 0.3) × 103, (5.3 ± 0.6) × 102. The mechanistic implications of the observed kinetic effects for these noncomplexing anions are discussed.
- Diaddario Jr., Leonard L.,Ochrymowycz,Rorabacher
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p. 2347 - 2353
(2008/10/08)
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- Kinetics of the bis(2,9-dimethyl-1,10-phenanthroline)copper(I/II) self-exchange reaction in solution
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The rate of the Cu(dmp)2+/2+ electron-transfer reaction has been measured by 1H NMR spectroscopy in the perdeuterated solvents water (with the chloride salts), acetonitrile, and acetone (with the CF3SO3- salts). The respective kinetic parameters kex298/kg mol-1 s-1, ΔH*/kJ mol-1, and ΔS*/J K-1 mol-1, at ionic strength I/mol kg-1, are as follows: for D2O, 2.0 × 105, 24, and -63, at 0.002; for CD3CN, 4.9 × 103, 29.6, and -75, at 0.1; for (CD3)2CO, 3.0 × 103, 29.2, and -80, at 0.1. For acetonitrile and acetone, respectively, variable-pressure studies gave ΔV* = -3.4 and -7.8 cm3 mol-1. No significant concentration dependences of these parameters were observed. With these data, the measured rate of the oxidation of RuII(CF3COCHCOCF3)3- by Cu(dmp)22+ in CH3CN can be satisfactorily accounted for, by using the Marcus cross relation. There is evidence that the CuII complex contains coordinated solvent in solution; with this qualification, the characteristics of the electron-transfer reactions conform to the Marcus outer-sphere adiabatic model.
- Doine, Hideo,Yano, Yoshiko,Swaddle, Thomas W.
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p. 2319 - 2322
(2008/10/08)
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- Synthesis and characterization of a copper(I) triflate complex of 1,2:5,6:9,10-tribenzocyclododeca-1,5,9-triene-3,7,11-triyne
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A copper(I) triflate complex of 1,2:5,6:9,10-tribenzocyclododeca-1,5,9-triene-3,7,11-triyne (1) has been synthesized and characterized by X-ray crystallography, NMR and IR spectroscopies, and elemental analysis. The copper(I) ion of the complex 3 is chelated by the three alkynes of 1 and semicoordinated by an oxygen of the triflate anion. Complex 3 disproportionates to Cu(0) and Cu(II) in THF solution.
- Ferrara, Joseph D.,Tessier-Youngs, Claire,Youngs, Wiley J.
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p. 676 - 678
(2008/10/08)
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- Synthesis, characterization, and reactivity of copper(I) and copper(II) complexes of N,N′-bis(3-(2-thenylidenimino)propyl)piperazine (tipp) and N,N′-bis(3-(2-thenylamino)propyl)piperazine (tapp). Crystal structure of [Cu(tapp)][ClO4]2
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Copper(I) and copper(II) complexes of the new ligands N,N′-bis(3-(2-thenylidenimino)propyl)piperazine (tipp) and N,N′-bis(3-(2-thenylamino)propyl)piperaZine (tapp) have been synthesized. Complexes of the type [Cu(ligand)] [ClO4], ligand = tipp or tapp, have been prepared by the reaction of tipp or tapp with [Cu(MeCN)4][ClO4]. Complexes of the type [Cu(ligand)]X2 (X = ClO4-, NO3-, OSO2CF3-) have been prepared by the reaction of tipp or tapp with Cu(ClO4)2·6H2O, Cu(NO3)2·3H2O or Cu(OSO2CF3)2, respectively. The complexes have been characterized by conductivity measurements and by infrared, electronic, and EPR spectroscopy. In addition the structure of [Cu(tapp)] [ClO4]2 has been determined by diffraction methods. The [Cu(ligand)][ClO4]2 complexes display CuN4 coordination in solution and in the solid state. The nitrate complexes are properly described as [Cu(ligand) (ONO2)][NO3] in both solution and the solid state, with CuN4O coordination While the CuIIOSO2CF3 salts show CuN4O coordination in the solid state, they display CuN4 coordination in solution For the Cu(I) complexes the Cu(tapp)+ ion is rapidly oxidized in solution while the Cu(tipp) ion is more stable and probably displays CuN2S2 or CuN4S2 coordination. For both the Cu(I) and Cu(II) complexes the tipp derivatives undergo the expected hydrolysis of the imine linkages in solution. In the solid state the Cu(tapp)2+ ion of [Cu(tapp)][ClO4]2 displays a CuN4 coordination that is severely distorted from square planar with N-Cu-N angles as small as 74.2 (2)° and deviations from the CuN4 plane as large as 0.397 (4) A?. The disposition of the thiophene S atoms about the Cu ion is suggestive of an incipient CuN4S2 coordination. The material crystallizes with 4 formula units in space group C2v17-C2ca of the orthorhombic system in a cell of dimensions a = 11.302 (5), b = 16.239 (7), and c = 13.948(6) A?. A crystallographic twofold axis is imposed on the cation. The structure has been refined to a final R index on F2 of 0.079, on the basis of 167 variables and 2331 observations collected at -150°C.
- Casella, Luigi,Ibers, James A.
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p. 2438 - 2448
(2008/10/08)
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- DIE ELEKTROFLUORIERUNG VON CHLORMETHYLSULFOCHLORID
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The electrochemical fluorination of ClCH2SO2Cl was studied.The main products were CF4, CF3Cl, SO2F2, SF6, CF3SO2F and ClCF2SO2F.Also minor amounts of CF3H and CF2HCl were formed as well as traces of CFH2Cl and CF2H2 under certain conditions.The yield of ClCF2SO2F increased with descending temperature, concentration and current density.
- Sartori, P.,Habel, W.
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p. 265 - 276
(2007/10/02)
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