34946-82-2

Usage

Uses

1. Used in Organic Synthesis:
COPPER(II) TRIFLUOROMETHANESULFONATE is used as a catalyst for promoting dehydration of alcohols and diols to alkenes at ambient temperatures. This application is particularly useful in the synthesis of various organic compounds.
2. Used in Generating Carbenoid Species:
COPPER(II) TRIFLUOROMETHANESULFONATE is used as a catalyst to generate carbenoid species from α-diazo esters and ketones, via in situ reduction to the Cu(I) species. This process is essential in the formation of complex organic molecules.
3. Used in the Synthesis of Aziridines:
COPPER(II) TRIFLUOROMETHANESULFONATE is used as a catalyst to promote the reaction between diazo esters and imines, resulting in the formation of aziridines. Aziridines are important intermediates in the synthesis of various pharmaceuticals and agrochemicals.
4. Used in Aldol Condensation:
COPPER(II) TRIFLUOROMETHANESULFONATE is used as a catalyst for syn-selective aldol condensation of (Z)-silyl enol ethers with aldehydes. This selective reaction is crucial in the synthesis of specific organic compounds with desired stereochemistry.
5. Used in Friedel-Crafts Alkylation:
COPPER(II) TRIFLUOROMETHANESULFONATE is used as a catalyst in Friedel-Crafts alkylation, a reaction that involves the addition of an alkyl group to an aromatic ring. This process is widely used in the production of various aromatic compounds.
6. Used in Acylation Reactions of Aromatics:
COPPER(II) TRIFLUOROMETHANESULFONATE is used as a catalyst for acylation reactions of aromatics, which involve the introduction of an acyl group to an aromatic ring. This reaction is essential in the synthesis of various aromatic compounds and derivatives.
7. Used in the Addition of Trimethylsilyl Cyanide to Carbonyl Compounds:
COPPER(II) TRIFLUOROMETHANESULFONATE is used as a catalyst in the addition of trimethylsilyl cyanide to carbonyl compounds. This reaction is important in the synthesis of various organic compounds, including those with potential applications in the pharmaceutical and chemical industries.

Reaction

Ring-Opening of epoxides and aziridines. Asymmetric conjugate addition of organozinc reagents to α,β-unsaturated ketones. Electrophilic addition of olefins. Asymmetric aziridination of olefins. Asymmetric cycloadditions and aldol condensations. Asymmetric Kharasch oxidation. Asymmetric Michael addition of enamides. Asymmetric O-H or O-R insertion reactions. Enantioselective intramolecular aminooxygenation of alkenes. Enantioselective addition of dialkylzinc reagents to N-acylpyridinium salts. Pd-catalyzed C-H functionalizations of oximes with arylboronic acids. Used as a Lewis acid in the Nazarov cyclization. Catalyst in the diacetoxylation olefins. Catalyst in the meta-selective direct arylation of α-aryl carbonyl compounds. Catalyst in the three-component coupling of amines, aldehydes, and alkynes.

Purification Methods

Dissolve it in MeCN, add dry Et2O until cloudy and cool at -20o in a freezer. The light blue precipitate is collected and dried in a vacuum oven at 130o/20mm for 8hours. It has 737nm ( 22.4 max M1cm -1) in AcOH. [Salomon & Kochi J Am Chem Soc 95 330 1973]. It has also been dried in a vessel at 0.1Torr by heating with a Fischer burner [Andrist et al. J Org Chem 43 3422 1978]. It has been dried at 110-120o/5mm for 1hour before use and forms a *benzene complex which should be handled in a dry box because it is air sensitive [Kobayashi et al. Chem Pharm Bull Jpn 28 262 1980, Salomon & Kochi J Am Chem Soc 95 330 1973]. [Beilstein 3 IV 34.]

InChI:InChI=1/2CF3O2S.Cu/c2*2-1(3,4)7(5)6;/q2*-1;+2

Upstream product

• 1493-13-6 trifluorormethanesulfonic acid 
• 10170-69-1 dimanganese decacarbonyl 
• 75-05-8 acetonitrile 
• 14285-68-8 decacarbonyldirhenium⁽⁰⁾ 
• 358-23-6 trifluoromethylsulfonic anhydride 
• 14693-30-2 decacarbonylmanganeserhenium 
• 12775-96-1 copper 
• 2923-28-6 silver trifluoromethanesulfonate 
• 20427-59-2 copper hydroxide 
• 533-01-7 copper(II) benzoate 
• 106568-03-0 copper(I) triflate 1,2:5,6:9,10-tribenzocyclododeca-1,5,9-triene-3,7,11-triyne complex 
• 57673-86-6 copper(II)(1,4,8,11-tetrathiacyclotetradecane) trifluoromethanesulfonate 

Downstream Products

• 97-41-6 ethyl 2,2-dimethyl-3-(2-methylpropenyl)cyclopropanecarboxylate 
• 909806-21-9 CHF₃O₃S*C₂₂H₃₄N₂O₂S 
• 27674-37-9 (acetonitrile)pentacarbonylmanganese(I) cation 
• 34946-82-2 copper(I) triflate 
• 29421-17-8 Re(CO)5(CH₃CN)⁽¹⁺⁾ 

Relevant academic research and scientific papers

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

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.

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

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.

Copper-63 NMR line width study of the copper(I)-acetonitrile system

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.

Equilibrium and kinetics of the dinuclear complex formation between N,N′-ethylenebis(salicylideneiminato)copper(II) and metal(II,I) ions in acetonitrile

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.

Reaction of copper(II) with ferrocene and 1,1′-dimethylferrocene in aqueoys acetonitrile: The copper(II/I) self-exchange rate

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.

On the quenching of MLCTRe-bpy luminescence by Cu(II) species in Re(I) polymer micelles

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.

EXAFS Study on the Coordination Chemistry of the Solvated Copper(II) Ion in a Series of Oxygen Donor Solvents

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.

Training a Constitutional Dynamic Network for Effector Recognition: Storage, Recall, and Erasing of Information

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.

A method of manufacturing a metal salt aminoalkylsulfonic Perfluoropolyalkyl

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

Copper mediated stereoselective synthesis of C-glycosides from unactivated alkynes

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.