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Versatility of the nature of the magnetic Cu(II)-U(IV) interaction. Syntheses, crystal structures and magnetic properties of Cu2U and CuU compounds

Treatment of [M(H2Li)] with U(acac)4 in refluxing pyridine led to the formation of the trinuclear complexes [{MLi(py)x}2U] [L1 = N,N?-bis(3-hydroxysalicylidene)-2,2-dimethyl-1,3-propanediamine and M = Ni, Cu or Zn; L2 = N,N?-bis(3-hydroxysalicylidene)-1,3-propanediamine and M = Cu or Zn; L3 = N,N?-bis(3-hydroxysalicylidene)-2-methyl-1,2-propanediamine and M = Ni, Cu or Zn; x = 0 or 1]. The dinuclear compounds [ML3(py)U(acac)2] (M = Cu, Zn) were isolated from the reaction of [M(H2L3)] and U(acac)4 in pyridine at 60C. The crystal structures of the trinuclear complexes are built up by two orthogonal MLi(py)x units which are linked to the central uranium ion by the two pairs of oxygen atoms of the Schiff base ligand; the U(IV) ion is found in the same dodecahedral configuration but the Cu(II) ion coordination geometry and the Cu … U distance are different by passing from L1 or L2 to L3, due to the shortening of the diimino chain of L3. These geometrical parameters seem to have a great influence on the magnetic behaviour of the complexes since the Cu-U coupling in [{CuLi(py)x}2U] (i = 1, 2) is ferromagnetic while it is antiferromagnetic in [{CuL3(py)x}2U]. In the compounds [{CuL3(py)x}2U] and [CuL3(py)U(acac)2], the Cu coordination and the Cu … U distance are very similar, and both exhibit an antiferromagnetic interaction.

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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(II)-mediated oxime-nitrile coupling in non-aqueous solutions: Synthetic, structural and magnetic studies of the copper(II)-salicylaldehyde oxime reaction system

The reactions of salicylaldehyde oxime (H2salox) with Cu II precursors yielded the known complexes [Cu(Hsalox)2] (1) and [Cu(Hsalox)2]n (2), as well as complexes [Cu 3(salox)(L1)(L2)]¡¤MeCN (3¡¤MeCN), [CuCl(L1)] (4) and [Cu2Na(O2CMe) 5(HO2CMe)]n (5), where L1 – = o-O-C6H4-CHNO-C(CH3)NH and L23- = o-O-C6H4-CHNO-C(o-O-C 6H4)N. L1- was formed in situ via the nucleophilic addition of the oximato O-atom of salox2- to the unsaturated nitrile group of the MeCN reaction solvent. L2 3- is also formed in situ probably through the nucleophilic attack of the oximato O-atom to the unsaturated nitrile group of salicylnitrile; the latter, although not directly added to the reaction mixture, can be produced via the dehydration of salox2-. Compounds 1 and 2 contain Hsalox – bound to the metal center in two different coordination modes; they both contain the same mononuclear unit, however a 2D network is generated in 2 due to a relatively long Cu-Ooximato bond. Compound 3 contains three different ligands, i.e. salox2-, L1- and L 23-, which act as mu3-kappa2O: kappaO?:kappaN, kappaO:kappaN:kappaN? and mu3-kappa2O:kappa2N:kappaO?: kappaN?, respectively, whereas 4 consists of a square planar Cu II atom bound to a kappaO:kappaN:kappaN? L 1- and a chloride ion. Compound 5 consists of dinuclear [Cu2(O2CMe)5(HO2CMe)]- units and Na+ ions assembled into an overall 3D network structure. Magnetic susceptibility measurements from polycrystalline samples of 2 and 5 gave best-fit parameters J = +0.36 cm-1 (H = -JS? iS?j) and J = -360 cm-1, zj = +20 cm -1 (H = -JS?iS?j – zJ?S z?S?z), 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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Total synthesis of apicularen a through transannular pyran formation

A macrocyclization-transannulation strategy is the crux of an efficient total synthesis of the benzolactone enamide apicularen A (see scheme; Bn = benzyl). Key steps include a four-component coupling, a Stille cross-coupling to introduce the aromatic moiety, and the formation of the enamide from a hemiaminal. The size-selective macrolactonization of the ethoxyvinyl ester shown was followed by transannular etherification in excellent yield.

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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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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.SDS of cas: 13395-16-9, Name is Bis(acetylacetone)copper, molecular formula is C10H16CuO4, SDS of cas: 13395-16-9. In a Article, authors is Aggarwal, R. C.£¬once mentioned of SDS of cas: 13395-16-9

Pyridinecarboxamide Complexes of Co(II), Ni(II), Cu(II), Zn(II) and VO(IV) Acetylacetonates

Pyridinecarboxamide complexes of the types M(acac)2L2 and M'(acac)2L have been prepared and characterised on the basis of elemental analyses, molar conductivity, magnetic susceptibility, electronic, ESR (for Cu and VO complexes only) and IR spectral measurements.

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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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Stabilizing CuPd Nanoparticles via CuPd Coupling to WO2.72 Nanorods in Electrochemical Oxidation of Formic Acid

Stabilizing a 3d-transition metal component M from an MPd alloy structure in an acidic environment is key to the enhancement of MPd catalysis for various reactions. Here we demonstrate a strategy to stabilize Cu in 5 nm CuPd nanoparticles (NPs) by coupling the CuPd NPs with perovskite-type WO2.72 nanorods (NRs). The CuPd NPs are prepared by controlled diffusion of Cu into Pd NPs, and the coupled CuPd/WO2.72 are synthesized by growing WO2.72 NRs in the presence of CuPd NPs. The CuPd/WO2.72 can stabilize Cu in 0.1 M HClO4 solution and, as a result, they show Cu, Pd composition dependent activity for the electrochemical oxidation of formic acid in 0.1 M HClO4 + 0.1 M HCOOH. Among three different CuPd/WO2.72 studied, the Cu48Pd52/WO2.72 is the most efficient catalyst, with its mass activity reaching 2086 mA/mgPd in a broad potential range of 0.40 to 0.80 V (vs RHE) and staying at this value after the 12 h chronoamperometry test at 0.40 V. The synthesis can be extended to obtain other MPd/WO2.72 (M = Fe, Co, Ni), making it possible to study MPd-WO2.72 interactions and MPd stabilization on enhancing MPd catalysis for various chemical reactions.

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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-catalyzed intramolecular dehydrogenative aminooxygenation: Direct access to formyl-substituted aromatic N-heterocycles

A direct synthesis of carbaldehydes through intramolecular dehydrogenative aminooxygenation has been developed. The process uses a catalytic amount of copper(II) in DMF or DMA under oxygen and does not require additional oxidants (see scheme). Mechanistic studies suggest that the carbonyl oxygen atom of the aldehyde is derived from oxygen through a copper-mediated oxygen activation process via a peroxy-copper(III) intermediate. Copyright

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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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Compositionally tunable Cu2ZnSn(S1-xSe x)4 nanocrystals: Probing the effect of Se-inclusion in mixed chalcogenide thin films

Nanocrystals of multicomponent chalcogenides, such as Cu 2ZnSnS4 (CZTS), are potential building blocks for low-cost thin-film photovoltaics (PVs). CZTS PV devices with modest efficiencies have been realized through postdeposition annealing at high temperatures in Se vapor. However, little is known about the precise role of Se in the CZTS system. We report the direct solution-phase synthesis and characterization of Cu 2ZnSn(S1-xSex)4 nanocrystals (0 ? x ? 1) with the aim of probing the role of Se incorporation into CZTS. Our results indicate that increasing the amount of Se increases the lattice parameters, slightly decreases the band gap, and most importantly increases the electrical conductivity of the nanocrystals without a need for annealing.

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

 

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Effect of transition metal diketonates on oxidation of sunflower-seed oil

Effect of transition metal (Mn, Fe, Co, Ni, Cu, Zn) diketonates on oxidation of sunflower-seed oil with atmospheric oxygen was studied.

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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”