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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”

 

Brief introduction of Bis(acetylacetone)copper

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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”

 

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A process for the preparation of the nitrile compound of the carbonitriding method (by machine translation)

The present invention provides a method for the preparation of nitrile compounds cyanide, the organic halide or to be halide with a readily available and inexpensive CO2 , NH3 And a reducing agent, in the presence of a transition metal catalyst of selective carbonitriding reaction, to obtain the target product with a nitrile compound. In the present invention using a brand-new reaction route, through the metal catalytic CO2 And the NH3 The reaction, “one-pot” directly realize halide and intended to halide removing (intended to be) […], avoids the need to use the traditional cyano reaction equivalent highly toxic cyanide issues, at the same time provides a direct, the new method of preparing isotope-labeled nitrile compounds, can be used for medical, tracing, in biological and pharmaceutical research. (by machine translation)

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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, characterization and fungicidal activity of binary and ternary metal(II) complexes derived from 4,4?-((4-nitro-1,2-phenylene) bis(azanylylidene))bis(3-(hydroxyimino)pentan-2-one)

Ternary copper(II) and binary copper(II), nickel(II) and cobalt(II) complexes derived from 4,4?-((4-nitro-1,2-phenylene)bis(azanylylidene))bis(3-(hydroxyimino)pentan-2-one) (H2L) were synthesized and characterized by elemental and thermal analyses, IR, UV-Vis. and 1H NMR spectroscopy, conductivity and magnetic moments measurements. The analytical and spectral data showed that, the ligand acts as dibasic tetradentate or dibasic hexadentate bonding to the metal ion via the two-imine nitrogen, two nitrogen and/or oximato oxygen atoms of deprotonated oxime groups forming five and/or six rings including the metal ions. The complexes adopt either tetragonal distorted octahedral or square planar geometry around metal ions. The ESR spectra of the solid copper(II) complexes are characteristic to d9 configuration and having an axial symmetry type of a d(x2-y2) ground state. The g values confirmed the geometry is elongated tetragonal octahedral geometry with considerably ionic or covalent environment. The antifungal biological activity of the prepared compounds was studied using well diffusion method. The obtained results showed that, the ligand is biologically inactive while its metal complexes were more potent fungicides than the ligand and standard antifungal drug (Amphotericin B).

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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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Stereoselective synthesis of tetrahydropyran-3-ones by rearrangement of oxonium ylides generated from metal carbenoids

The synthesis of tetrahydropyran-3-ones by copper-catalysed reactions of diazo ketone tethered allylic ethers has been explored. Product distribution can be explained by the intermediacy of a free ylide or direct rearrangement of a metal-bound ylide equivalent.

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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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Oxyfunctionalization of hydrocarbons by in situ formed peracid or by metal assisted aerobic oxidation

The oxidation of hydrocarbons such as adamantane, cyclohexane, tetraline and indane has been investigated using the oxygen/3-methylbutanal system in the presence and in the absence of metal catalyst. The reactivity order reflects the facility of hydrogen abstraction from the substrate.

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