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3D supramolecular networks based on hydroxyl-rich Schiff-base copper(II) complexes

Reactions of the Schiff base ligand OH-C6H4-CH[dbnd]NC(CH2OH)3 (H4L) with copper(II) salts in various reaction media afforded complexes [Cu4(H2L)4]¡¤MeOH (1¡¤MeOH), [Cu2(O2CMe)2(H3L)2] (2), [Cu4(H2L)4(H2O)2]¡¤1.5dmf (3¡¤1.5dmf), [Cu4(H2L)4(H2O)]¡¤MeOH (4¡¤MeOH) and [Cu4(H2L)4]2¡¤2H2O¡¤7MeOH (5¡¤2H2O¡¤7MeOH). Compounds 1, 3 and 4 consist of neutral tetranuclear entities in which the CuII ions are coordinated by the tridentate Schiff base ligands, forming a tetranuclear Cu4O4 cubane-like configuration. Compound 5 contains similar cubane-like tetranuclear entities which are further linked through the hydroxyl groups of the ligands thus forming dimers of cubanes. Compound 2 contains a neutral dinuclear entity in which the CuII ions are bridged through the Schiff base and the acetate ligands, comprising distorted Cu2O2 core. The Schiff base ligand adopts five different coordination modes and two deprotonation states in the structures of 1?5 acting simultaneously as chelating and bridging agent between the metal ions. The lattice structures of 1?5 exhibit interesting 3D networks based on hydrogen bonded metal clusters and they are studied with Hirshfeld Surface analysis methods.

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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”

 

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Semicorrin Metal Complexes as Enantioselective Catalysts. Part 1. Synthesis of Chiral Semicorrin Ligands and General Concepts

An efficient synthesis of chiral semicorrin ligands is described (see 6-9, Schemes 2 and 3).Both enantiomers are readily obtained in enantiomerically pure form starting either from D- or L-pyroglutamic acid (1).Semicorrins of this type possess several features that make them attractive ligands for enantioselective control of metal-catalyzed reactions.Their structure is characterized by C2 symmetry, a conformationally rigid ligand system, and two stereogenic centers adjacent to the coordination sphere.In a metal complex, the two substituents at the stereogenic centers shield the metal atom from two opposite directions and, therefore, are expected to have a pronounced effect on the stereochemical course of a reaction occuring in the coordination sphere.The structure of these two substituents can be easily modified in a variety of ways.A series of (semicorrinato)copper(II) complexes (see 10-14, Scheme 4) has been prepared, and in one case (14), the three-dimensional structure has been determined by X-ray analysis (Fig. 1).

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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 CuO and Cu2O nano/microparticles from a single precursor: Effect of temperature on CuO/Cu2O formation and morphology dependent nitroarene reduction

CuO and Cu2O nano/microparticles with pure phases have been synthesized from the same precursor by a hydrothermal method. Hydrothermal heating of Cu(OAc)2 produced CuO at 125 C whereas pure Cu2O was obtained at 175 C. Heating at 150 C gave a CuO/Cu2O mixture. In contrast, Cu(acac)2 produced only Cu2O at all three temperatures. The pure phases of Cu2O and CuO nano/microparticles were confirmed by PXRD and XPS characterization. The mechanistic studies indicate that decomposition of the organic anion/ligand of the Cu-precursor played a key role in the formation of CuO/Cu2O nano/microparticles from Cu(OAc)2/Cu(acac)2. FE-SEM studies revealed the formation of CuO with a microsphere morphology (125 C) and a micro-cup for Cu2O at 175 C. Nanowires and micron-sized elliptical cylinders were observed for Cu2O synthesized from Cu(acac)2. However, calcination of Cu(OAc)2, Cu(acac)2 and Cu(NO3)2 at 500 C produced crystalline CuO nano/microparticles with various sizes and morphologies. Further, CuO nano/microparticles investigated for industrially important aromatic nitro to amine conversion showed morphology dependent nitro group reduction. Smaller spherical CuO nano/microparticles obtained from Cu(acac)2 exhibited the highest catalytic activity. The reusability studies indicate that CuO nano/microparticles can be used for up to six cycles. Thus we have presented a simple method to synthesize Cu2O or CuO from the same precursor and demonstrated the morphology dependent catalytic activity of CuO nano/microparticles.

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

 

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One of the oldest and most widely used commercial enzyme inhibitors is aspirin, name: Bis(acetylacetone)copper, which selectively inhibits one of the enzymes involved in the synthesis of molecules that trigger inflammation. you can also check out more blogs about 13395-16-9

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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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We¡¯ll also look at important developments in the pharmaceutical industry because understanding organic chemistry is important in understanding health, medicine, the role of 13395-16-9, and how the biochemistry of the body works.SDS of cas: 13395-16-9

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”