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T-shaped cationic CuI complexes with hemilabile PNP-type ligands

The versatile coordination behavior of the PNP ligands 1A (2,6-bis[(di-tert-butylphosphino)methyl]pyridine) and 1B (2,6- bis[(diphenylphosphino)methyl]pyridine) to CuI is described, whereby a hemilabile interaction of the pyridine N-donor atom to the copper center resulted in a rare T-shaped complex with 1A, while with 1B also a tetracoordinated species could be isolated. Theoretical calculations support the weak interaction of the pyridine N donor in 1A with the Cu center.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Copper-Catalyzed Electrophilic Thiolation of Organozinc Halides by Using N-Thiophthalimides Leading to Polyfunctional Thioethers

(Hetero)aryl, benzylic, and alkyl zinc halides were thiolated with N-thiophthalimides at 25 C within 1 h in the presence of 5?10 % Cu(OAc)2?H2O to furnish the corresponding polyfunctionalized thioethers in good yields. This electrophilic thiolation was extended to the introduction of trifluoromethylthio (SCF3), thiocyanate (SCN), and selenophenyl (SePh) groups. The utility of this method was shown in a seven-step synthesis of a potent cathepsin D inhibitor in 34 % overall yield.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Mono- or disubstituted 1,2,4,oxadiazoles which are substituted by at least 1-N-substituted carbamoyl group

1,2,4-Oxadiazoles having as 3- and 5-substituents a hydrogen atom, an aliphatic, cycloaliphatic, araliphatic, aryl or heterocyclic group, or a carbamoyl group of the formula — CONR1 R2 where R1 & R2 which can be the same or different, are hydrogen atoms or aliphatic, cycloaliphatic, araliphatic or aryl groups or, taken with the N atom, a heterocvolic ring; provided that at least one of the 3- or 5-substituents is an N-substituted carbamoyl group. Antimicrobial activity, and particularly antiviral, antiparasitic and antibacterial activity is shown in this group. The corresponding oxadiazolins are also described and are useful intermediates in the preparation of the oxadiazoles.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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A 12-connected dodecanuclear copper cluster with yellow luminescence

The 3-D 12-connected metal-organic framework [Cu12Br2(CN) 6/2- (SCH3)6][Cu(SCH3)2], containing dodecanuclear copper clusters, has been solvothermally synthesized and exhibits efficient yellow luminescence. The emission mechanism was studied In detail to elucidate the relationship of the luminescent properties and crystal structures, which is helpful for the design and synthesis of more efficient luminescent materials.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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A solar cell sensitized with three different dyes

Construction of a semiconductor – dye heterostructure of the configuration n-TiO2/D1/p-CuSCN/D2/p-CuSCN/D 3/p-CuSCN. (n-TiO2 is the nanocrystalline TiO2 film deposited on conducting glass, p-CuSCN = ultra-thin (?2 nm) layers of Cu(I) thiocyanate, p-CuSCN = thick layer of p-CuSCN, D 1 = Fast Green, D2 = Rhodamine 6G and D3 = Acridine Yellow) is described. It is found that this heterojunction generates photovoltaic response to light absorption by all the three dyes. The mechanism involved is suggested to be transfer of electrons to n-TiO2 and holes to p-CuSCN via tunneling. This technique could be a strategy to broaden the spectral response and enhance the efficiency of dye-sensitized solar cells.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Synthesis, spectroscopic and structural characterization of some novel adducts of copper(II) salts with unidentate nitrogen bases

Syntheses, spectroscopic characterization and single crystal X-ray studies are reported for a number of complexes of copper(II) salts with simple monodentate nitrogen bases. The 1:4 adduct of copper(II) sulfate with 3,5-dimethylpyridine (m2py) CuSO4·4m2py, takes the form [(O3SO)Cu(m2py)4], the Cu-O vector of the square-pyramidal coordination environment being disposed on the 4-axis in tetragonal space group P4/n. The complex CuCO3· Cu(NCS)2·4py is a linear polymer, taking the form ?O·Cu(py)2·O·C{O·Cu(py) 2(NCS)2}·O·Cu(py)2? (etc.), all atoms lying in the mirror plane of space group Pnma, excepting the pair of ‘py’ (pyridine) ligands disposed to either side. In Cu(OH)I·3/ 4I2·2py·1/2MeCN ? [{(py)2Cu(OH)} 4](I3)3I·2MeCN a novel cubanoid tetranuclear cation is found (2-symmetry). The EPR spectra of the above compounds show a trend in the anisotropy of the g-values that correlates well with the crystal structures. Obtained only in small quantities but supported by single crystal X-ray studies are the adduct of Cu(OH)Cl with pyrrolidine (pyrr), Cu(OH)Cl:pyrr (1:3), which takes the centrosymmetric binuclear form [(pyrr)3Cu(mu-OH)2Cu(pyrr)3]Cl2, the copper atom being disposed in a distorted trigonal bipyramidal array, and the adduct 3CuCl2·CuO·4quin, [Cu4Cl 6O(quin)4]Cl2, which contains the familiar Cu4Cl6O core with monodentate quinuclidine (quin) attached to the copper atoms; this compound crystallizes in the cubic space group 4?3m.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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COMBINATIONS OF 4-BROMO-2-(4-CHLOROPHENYL)-5-(TRIFLUOROMETHYL)-1H-PYRROLE-3-CARBONITRILE AND METAL COMPOUNDS

The present invention relates to combinations of 4-bromo-2-(4-chloro-phenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, or a salt thereof, and copper or zinc compounds which provide an improved protecting effect against fouling organisms. More particularly, the present invention relates to compositions comprising a combination of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, or a salt thereof, together with one or more copper or zinc compounds selected from Cu2O, Cu(OH)2, CuSO4, copper pyrithione, CuSCN, CuCO3, ZnO, ZnCl2, ZnSO4, zineb, and zinc pyrithione; in respective proportions to provide a synergistic effect against fouling organisms and the use of these compositions for protecting materials against fouling organisms. This invention thus relates to the field of protection of materials, such as underwater objects, protection of wood, wood products, biodegradable materials and coatings.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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In situ imaging Raman spectroscopy of electrochemically deposited CuSCN

Imaging Raman spectroscopy is explored as a new tool for in situ studies of electrochemical systems. The technique provides a spatially resolved view of molecular species present along a focused laser line. The capabilities of our system are demonstrated using an electrodeposited thin film of CuSCN plated on a cylindrical platinum electrode. It is shown that line-imaging Raman spectroscopy is able to measure the properties of the thin film deposit while simultaneously monitoring the concentration of solution species within ? 1 mm of the surface. The Raman image presented here has a spatial resolution of ?6 mum and a spectral resolution of 24 cm-1, though neither constitutes resolution limits of the instrument.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Copper-catalyzed oxidative C-O coupling by direct C-H bond activation of formamides: Synthesis of enol carbamates and 2-carbonyl-substituted phenol carbamates

Formamide C-H bond activation has been achieved under oxidative conditions, using a copper catalyst and tert-butyl hydroperoxide (TBHP) as the external oxidant (see scheme). This oxidative coupling of a range of dialkyl formamides provides an easy, phosgene-free route for the selective synthesis of Z-enol carbamates and 2-carbonyl-substituted phenol carbamates in high yields. Copyright

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Copper(I)-mediated novel thiocyanation of nonactivated aryl iodides

Various aryl thiocyanates 2 were easily prepared in acceptable yields by heating aryl iodides 1 with cuprate complex K[Cu(SCN)2] in N,N-dimethylformamide (DMF).

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”