Top Picks: new discover of Bis(acetylacetone)copper

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Ionic liquid mediated Cu-catalyzed cascade oxa-Michael-oxidation: Efficient synthesis of flavones under mild reaction conditions

Flavonoids are a class of natural products, found in a wide range of vascular plants and dietary components. Their low toxicity and extensive biological activities, including anti-cancer and anti-bacterial, have made them attractive candidates to serve as therapeutic agents for many diseases. Herein, we disclose a highly efficient synthetic method of CuI-catalyzed cascade oxa-Michael-oxidation, using chalcones as substrates, mediated by the ionic liquid [bmim][NTf2] at a low temperature. This efficient synthetic method has demonstrated high synthetic utility and can afford flavones in good to high yields (up to 98%).

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

 

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Oxidation of white phosphorus by peroxides in aqueous and alcoholic solutions: mechanistic aspects and catalytic studies

The oxidation of white phosphorus by hydrogen peroxide or different organic peroxides (such as tert-butyl hydroperoxide, dibenzoylperoxide, 3-chloroperoxybenzoic acid) has been studied in both aqueous and alcoholic solutions under anaerobic conditions. Depending on the reaction conditions, P(I) (hypophosphorous acid), P(III) [phosphorous acid, mono- and dialkyl (or diaryl) hydrogen phosphonates] and P(V) [phosphoric acid or trialkyl (or triaryl) phosphates] derivatives are produced. The catalytic oxidative P-O coupling of P4 to water, aliphatic alcohols and phenol under mild reaction conditions is accomplished by using copper(I), copper(II) and vanadium(IV) complexes. Catalytic conversion of white phosphorus with complete efficiency and high selectivity for monoalkyl hydrogen phosphonates (>95%) may be achieved using 3-ClC6H4C(O)OOH as oxidant under optimized conditions. An identical radical mechanism is suggested to account for both the stoichiometric and the catalytic oxidative hydroxydation, alkoxydation and phenoxydation of white phosphorus promoted by peroxides in both aqueous biphasic conditions and organic solutions.

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

 

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Influence of the counter anion and solvent in the structure of copper derivatives with the 2,3-bis(2-pyridyl)pyrazine ligand

Several compounds have been isolated from the reaction between different copper bis(acetylacetonato) derivatives and the potentially bridging ligand 2,3-bis(2-pyridyl)pyrazine (bppz). A compound of formula [Cu(tfacac) 2(bppz)] (1) is obtained when the substituted trifluoromethylacetylacetonato is used. The use of different anions and the unsubstituted acetylacetonato give rise to new derivatives of general formula [{Cu(acac))2(mu-bppz)2]X2 (X– BF4-, 2; PF6-, 3; BPh 4-, 4). In these compounds the bppz ligand is acting as a bridge by chelating one copper atom and bonding monodentate a second copper atom. The presence of anions with different coordination abilities introduces variations in the copper environment and geometry. When the non-coordinating tetraphenylborate is used different compounds depending on the nature of the solvent are obtained. The dimer 4 was isolated from a methanol/chloroform mixture, while in the absence of chloroform the monomeric compound of formula [Cu(acac)(bppz)(ROH)](BPh4)-ROH (ROH=MeOH, 5) was obtained. When ethanol was used instead of methanol the analogous derivative 6 (R=EtOH) was isolated. Both species show a mononuclear structure with the copper atom five-coordinated by the chelating acac and bppz ligands and one hydroxo group occupying the apical position. A similar environment for the copper appears in [Cu(tfacac)(bppz)(MeOH)](BPh4), 7, which shows a dimeric structure through hydrogen bonds interactions. The magnetic susceptibility data of the dimeric compounds show very weak antiferromagnetic interactions between the copper atoms, an expected fact since the bridging bppz ligand is not planar but the monodentate pyridine is more or less perpendicular to the other two aromatic rings, precluding the spin exchange via the it ligand electrons.

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

 

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Copper thin films prepared by chemical vapour deposition from copper (II) acetylacetonate

Copper thin films were prepared by a low-temperature atmospheric pressure chemical vapour deposition method. The raw material was copper (II) acetylacetonate. At a reaction temperature above 220 C, polycrystalline copper films can be obtained by hydrogen reduction of the raw material. The resistivity of the film was close to that for bulk copper.

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

 

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Synthesis and crystal structure of tetra- and hexanuclear uranium(IV) complexes with hexadentate compartmental Schiff-base ligands

Treatment of UCl4 with the hexadentate Schiff bases H 2L? in thf gave the expected [UL?Cl2(thf)] complexes [H2L? = N,N?-bis(3-methoxysalicylidene)-R and R = 2,2-dimethyl-1,3-propanediamine (i = 1), R = 1,3-propanediamine (i = 2), R = 2-amino-benzylamine (i = 3), R = 2-methyl-1,2-propanediamine (i = 4), R = 1,2-phenylenediamine (i = 5)]. The crystal structure of (UL4Cl 2(thf)] (4) shows the metal in a quite perfect pentagonal bipyramidal configuration, with the two Cl atoms in apical positions. Reaction of UCl 4 with H4L? in pyridine did not afford the mononuclear products [U(H2L?)Cl2(py)x] but gave instead polynuclear complexes [H4L? = N,N?-bis(3-hydroxysalicylidene)-R and R = 1,3-propanediamine (i = 6), R = 2-amino-benzylamine (i = 7) or R = 2-methyl-1,2-propanediamine (i = 8)]. In the presence of H4L6 and H4L7 in pyridine, UCl4 was transformed in a serendipitous and reproducible manner into the tetranuclear U(IV) complexes [Hpy]2[U 4(L6)2(H2L6) 2Cl6] (6a) and [Hpy]2[U4(L 7)2(H2L7)2Cl 6][U4(L7)2(H2L 7)2 Cl4(py)2] (7), respectively. Treatment of UCl4 with [Zn(H2L6)] led to the formation of the neutral compound [U4(L6) 2(H2L6)2Cl4(py) 2] (6b). The hexanuclear complex [Hpy]2[U 6(L8)4Cl10(py)4] (8) was obtained by reaction of UCl4 and H4L8. The centrosymmetric crystal structures of 6a¡¤2HpyCl¡¤2py, 6b¡¤6py, 7¡¤16py and 8¡¤6py illustrate the potential of Schiff bases as associating ligands for the design of polynuclear assemblies.

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

 

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Magnetic, Spectral and Thermal Studies on Some Mixed Ligand Complexes of Copper(II) and Nickel(II)

Several mixed ligand complexes of copper(II) and nickel(II) having the compositions and , where aaH is acetylacetone, tcaH is trichloroacetic acid; L is gamma-picoline, imidazole, 2-picoline-N-oxide or thiourea and M is Cu(II) or Ni(II), have been isolated and characterised on the basis of their analyses, molar conductance, magnetic susceptibility, infrared, electronic spectral data and thermogravimetric measurements.The infrared spectra reveal the presence of uninegative bidentate acetyl acetonate and trichloroacetate groups in all these complexes.As the temperature increases, the mixed ligand complexes start decomposing with the loss of neutral donor ligand, followed by trichloroacetate ion and acetylacetonate ion in definite steps and ultimately forming MO at 600-675 deg .Square planar, tetrahedral, distorted octahedral and octahedral structures have been proposed for the complexes, , , and , respectively.

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

 

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Mesoporous Hollow Cu-Ni Alloy Nanocage from Core-Shell Cu@Ni Nanocube for Efficient Hydrogen Evolution Reaction

We have created a facial self-templated method to synthesize three distinct nanostructures, including the unique edge-cut Cu@Ni nanocubes, edge-notched Cu@Ni nanocubes, and mesoporous Cu-Ni nanocages by selective wet chemical etching method. Moreover, in the synthesis process, the corners of edge-cut Cu@Ni nanocubes and mesoporous Cu-Ni nanocages can be etched to produce the highly catalytically active (111) facets. Impressively, compared to edge-notched Cu@Ni nanocubes and edge-cut Cu@Ni nanocubes, the Cu-Ni nanocages exhibit higher electrocatalytic activity in the hydrogen evolution reaction (HER) under alkaline conditions. When obtained overpotential is 140 mV, the current density can reach 10 mA cm-2 meanwhile, the corresponding Tafel slope is 79 mV dec-1. Moreover, from the calculation results of density functional theory (DFT), it can be found that the reason why the activity of pure Ni is lower than that of Cu-Ni alloy is that the adsorption energy of the intermediate state (adsorbed H?) is too strong. Meanwhile the Gibbs free-energy (|DeltaGH?|) of (111) facets is smaller than that of (100) facets, which brings more active sites or adsorbs more hydrogen.

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

 

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Transition metal complexes containing the S(NtBu)42- tetraimidosulfate dianion

Three novel metal complexes [(acac)2Cu2(NtBu)4S] (3), [Li(thf)4]2[I4Cd2(NtBu)4S] (4) and [(thf)2Li{(SiMe3)2N}Zn(NtBu)4S] (5) are prepared from the intended transmetalation of the dilithium complex of N,N?,N??,N???-tetrakis(tert-butyl)tetraimidosulfate [(thf)4Li2(NtBu)4S] (1). The two lithium cations are replaced by either the cationic (acac)Cu(ii) moiety, the neutral I2Cd(ii) residue or only a single lithium cation is substituted by the cationic (Me3Si)2NZn(ii) fragment. The complexes show two main results: first the S(NtBu)42- tetrahedron can serve as a ligand to transition metals from the soft Cu(ii) to the harder Zn(ii) at opposite sides and second the S-N bond distances vary only marginally in response to the various metals and the four distances constantly sum up to 6.38(2) A. Hence the electropositive sulfur atom responds by internal shift to the metal-polarized negative charge at the outside of the S(NR)42- tetrahedron. This journal is

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

 

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Bis-copper(II) Complex of Triply-linked Corrole Dimer and Its Dication

Copper complexes of corroles have recently been a subject of keen interest due to their ligand non-innocent character and unique redox properties. Here we investigated bis-copper complex of a triply-linked corrole dimer that serves as a pair of divalent metal ligands but can be reduced to a pair of trivalent metal ligands. Reaction of triply-linked corrole dimer 2 with Cu(acac)2 (acac=acetylacetonate) gave bis-copper(II) complex 2Cu as a highly planar molecule with a mean-plane deviation value of 0.020 A, where the two copper ions were revealed to be divalent by ESR, SQUID, and XPS methods. Oxidation of 2Cu with two equivalents of AgBF4 gave complex 3Cu, which was characterized as a bis-copper(II) complex of a dicationic triply-linked corrole dimer not as the corresponding bis-copper(III) complex. In accord with this assignment, the structural parameters around the copper ions were revealed to be quite similar for 2Cu and 3Cu. Importantly, the magnetic spin?spin interaction differs depending on the redox-state of the ligand, being weak ferromagnetic in 2Cu and antiferromagnetic in 3Cu.

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

 

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Synthesis of 2-aminofurans and 2-unsubstituted furans via carbenoid-mediated [3 + 2] cycloaddition

An efficient dual synthetic manifold for 2-aminofurans and 2-unsubstituted furans has been developed. The carbenoid-mediated [3 + 2] cycloaddition of copper carbenoids with enamines provides 2-amino-2,3-dihydrofurans which serve as common intermediates for both 2-aminofurans and 2-unsubstituted furans. The Royal Society of Chemistry 2012.

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