34946-82-2

Basic information

• Product Name: COPPER(II) TRIFLUOROMETHANESULFONATE
• Synonyms: TRIFLUOROMETHANESULFONIC ACID COPPER SALT;TRIFLUOROMETHANESULFONIC ACID COPPER(II) SALT;COPPER TRIFLATE;COPPER(II) TRIFLATE;COPPER(II) TRIFLUOROMETHANESULFONATE;COPPER(II) TRIFLUOROMETHANESULPHONATE;CUPRIC TRIFLUOROMETHANESULFONATE;Copper (II) trifluoromethanesulfonate, (Copper triflate)
• CAS NO: 34946-82-2
• Molecular Formula: CCuF₃O₃S
• Molecular Weight: 361.68
• EINECS: 252-300-8
• Product Categories: Biochemistry;Catalysts for Organic Synthesis;Classes of Metal Compounds;Cu (Copper) Compounds;Homogeneous Catalysts;Metal Triflates;Reagents for Oligosaccharide Synthesis;Synthetic Organic Chemistry;Transition Metal Compounds;metal triflate compounds;triflate;Cu;OTf&NTf series
• Mol File: 34946-82-2.mol
• Article Data: 22

Chemical Properties

• Melting Point: ≥300 °C
• Boiling Point: 162 °C at 760 mmHg
• Appearance: White to slightly blue or light gray/Powder
• Storage Temp.: Inert atmosphere,Room Temperature
• Water Solubility: Soluble in water.
• Sensitive: Hygroscopic
• Stability: hygroscopic
• BRN: 4028198
• CAS DataBase Reference: COPPER(II) TRIFLUOROMETHANESULFONATE(CAS DataBase Reference)
• NIST Chemistry Reference: COPPER(II) TRIFLUOROMETHANESULFONATE(34946-82-2)
• EPA Substance Registry System: COPPER(II) TRIFLUOROMETHANESULFONATE(34946-82-2)

Safety Data

• Hazard Codes: C,Xi
• Statements: 34
• Safety Statements: 26-36/37/39-45-27
• RIDADR: UN 3261 8/PG 2
• WGK Germany: 3
• F: 3-10
• TSCA: No
• HazardClass: 8
• PackingGroup: III
• Hazardous Substances Data: 34946-82-2(Hazardous Substances Data)

Usage

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.

Chemical Properties

white to slightly blue or light grey cryst. powder

Uses

Copper(II) trifluoromethanesulfonate is a mild lewis acid. It is used as catalyst which promotes dehydration of alcohols and diols to alkenes at ambient temperatures. It is widely used to generate carbenoid species from ?-diazo esters and ketones, via in situ reduction to the Cu(I) species. It is also promotes the reaction between diazo esters and imines to give aziridines. It catalyzes syn-selective aldol condensation of (Z)-silyl enol ethers with aldehydes, Friedel-Crafts alkylation, acylation reactions of aromatics and addition of trimethylsilyl cyanide to carbonyl compounds.

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 
• 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 
• 848439-32-7 (Cu(H₂O)4(CF₃SO₃)2) 
• 57673-86-6 copper(II)(1,4,8,11-tetrathiacyclotetradecane) trifluoromethanesulfonate 

Downstream Products

• 97-41-6 ethyl 2,2-dimethyl-3-(2-methylpropenyl)cyclopropanecarboxylate 
• 27674-37-9 (acetonitrile)pentacarbonylmanganese(I) cation 
• 34946-82-2 copper(I) triflate 
• 29421-17-8 Re(CO)5(CH₃CN)⁽¹⁺⁾ 
• 14409-63-3 (octaethylporphyrin)copper(II) 
• 14172-91-9 (tetraphenylporphyrin)copper(II) 
• 113110-58-0 tetrakis(pyridine)bis(trifluoromethanesulfonato-O)copper(II) 
• 40410-87-5 phenyl ((Z)-prop-1-en-1-yl) sulfone 
• 19414-66-5 5,10,15,20-tetrakis(4-methylphenyl)porphyrinatocopper(II) 
• 495-71-6 phenacylacetophenone 
• 33454-82-9 lithium trifluoromethanesulfonate 

Relevant articles and documents

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.

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.

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.

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.