Discovery of Bis(acetylacetone)copper

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

 

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Cuboidal oxalate cluster complexes with the Mo3CuQ4 5+ cluster core (Q = S or Se): Synthesis, structure, and electrochemical properties

The reactions of the [Mo3(mu3-Q)(mu2- Q)3(H2O)3(C2O4) 3]2- complex (Q = S or Se) with CuX salts (X = Cl, Br, I, or SCN) in water produce the cuboidal heterometallic clusters [Mo 3(CuX)(mu3-Q)4(H2O) 3(C2O4)3]2-, which were isolated as the potassium and tetraphenylphosphonium salts. Two new compounds, K2[Mo3(CuI)(mu3-S)4(H 2O)3(C2O4)3]?6H 2O and (PPh4)2[Mo3(CuBr) (mu3-S)4(H2O)3(C2O 4)3]?7H2O, were structurally characterized. All compounds were characterized by elemental analysis and IR spectroscopy. The K2[Mo3(CuI)(mu3-Se) 4(H2O)3(C2O4) 3] compound was characterized by the 77Se NMR spectrum; the (PPh4)2[Mo3(CuI)(mu3-S) 4(H2O)3(C2O4) 3], (PPh4)2[Mo3(CuI) (mu3-Se)4(H2O)3(C 2O4)3] and K2[Mo3(CuSCN) (mu3-S)4(H2O)3(C2O 4)3]?7H2O compounds, by electrospray mass spectra.

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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(II) complex with acetylacetone phenylhydrazone: Synthesis, crystal structure, and thermal stability

The Cu(phac)2 complex was synthesized by the reaction of copper(II) acetate with acetylacetone phenylhydrazone (Hphac), and its crystal structure was established by X-ray diffraction: space group P21/c, a = 11.173(3) A, b = 8.267(2) A, c = 12.633(4) A, beta = 115.01(3), V = 1057.5(5) A3, Z = 4, R1 = 0.0476. The crystal structure of Cu(phac)2 consists of the centrosymmetrical mononuclear molecules. The central copper(II) ion is coordinated by two oxygen atoms and two nitrogen atoms of two acetylacetone phenylhydrazone ligands. The Cu(phac)2 molecules are linked in layers parallel to the Oyz plane. The oxygen atoms of the ketone fragment are involved in intermolecular bonding, which completes the coordination sphere of the central copper(II) ion to a substantially elongated octahedron. The thermal stability of the Cu(phac)2 complex was estimated under nitrogen at atmospheric pressure and in vacuo.

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

 

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Poly[[(pyridazine-kappaN)copper(I)]-mu3-thiocyanato- kappa3 N:S:S]

The crystal structure of the [Cu(NCS)-(C4H4N 2)]n was investigated. Each Cu atom was coordinated by one N atom of one pyridazine ligand and by one N and two S atoms of three symmetry-related thiocyanate anions within a distorted tetrahedron in the above compound. The compound was prepared by the reaction of CuSCN and pyridazine in acetonitrile in a teflon-lined steel autoclave at 373 K. It was observed that only one N atom of the pyridazine ligand was involved in Cu coordination. It was shown that the Cu atoms were connected via the thiocyanate anions, forming layers parallel to the ab plane.

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

 

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Transformation of inorganic sulfur into organic sulfur: A novel photoluminescent 3-D polymeric complex involving ligands in situ formation

The reaction of CuSCN with acetonitrile and methanol under solvothermal conditions yielded a novel 3-D polymeric photoluminescent complex containing dodecanuclear copper(I) clusters with methyl mercaptide. The synthesis involves in situ generation of ligands, which provides a model reaction to simulate the transformation of inorganic sulfur into organic sulfur under geothermic conditions.

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

 

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Structure-activity relationship of 3-substituted N-(pyridinylacetyl)-4- (8-chloro-5,6-dihydro-11H-benzo[5,6]cyclohepta[1,2-b]pyridin-11-ylidene)- piperidine inhibitors of farnesyl-protein transferase: Design and synthesis of in vivo active antitumor compounds

Novel tricyclic Ras farnesyl-protein transferase (FPT) inhibitors are described. A comprehensive structure-activity relationship (SAR) study of compounds arising from substitution at the 3-position of the tricyclic pyridine ring system has been explored. In the case of halogens, the chloro, bromo, and lode analogues 19, 22, and 28 were found to be equipotent. However, the fluoro analogue 17 was an order of magnitude less active. Whereas a small alkyl substituent such as a methyl group resulted in a very potent FPT inhibitor (SCH 56580), introduction of bulky substituents such as tert-butyl compound 33, or a phenyl group, compound 29, resulted in inactive FPT inhibitors. Polar groups at the 3-position such as amine 5, alkylamino 6, and hydroxyl 12 were less active. Whereas compound SCH 44342 did not show appreciable in vive antitumor activity, the 3-bromo-substituted pyridyl N- oxide amide analogue 38 was a potent FPT inhibitor that reduced tumor growth by 81% when administered q.i.d. at 50 mpk and 52% at 10 mpk. These compounds are nonpeptidic and do not contain sulfhydryl groups. They selectively inhibit FPT and not geranylgeranyl-protein transferase-1 (GGPT-1). They also inhibit H-Ras processing in COS monkey kidney cells and soft agar growth of Ras-transformed cells.

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

 

Top Picks: new discover of Cuprous thiocyanate

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Mass spectrometry of poly(methyl methacrylate) (PMMA) prepared by atom transfer radical polymerization (ATRP)

Poly(methyl methacrylate) (PMMA) was synthesized via atom transfer radical polymerization (ATRP). As a catalyst copper(I)thiocyanate (CuSCN) was used with N-n-pentyl-2-pyridylmethanimine as a ligand. Infrared spectroscopy and matrix assisted laser desorption ionization time-of-flight mass spectrometry were used to characterize the synthesized polymers. From this it was clear that at least to some extent thiocyanate was present as end groups of the PMMA chains. This observation is discussed in view of a phenomenon called halogen exchange, which has been reported before for bromine/chlorine exchange in ATRP.

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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 Self-Coupling of alpha-Amino Carbonyl Compounds for the Synthesis of Tetrasubstituted 1,4-Enediones

A protocol for the copper-catalyzed oxidative self-coupling of alpha-amino carbonyl compounds has been developed for the synthesis of tetrasubstituted 1,4-enediones (Z -isomers) in moderate to good yields through the cleavage of four sp 3 C-H bonds and the simultaneous formation of one C=C double bond in the alpha-amino carbonyl compound. The strategy has the advantages of using readily available starting materials and of high stereoselectivity.

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

 

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Thiocyanate hydrometallurgy for the recovery of gold. Part I: Chemical and thermodynamic considerations

Thiocyanate has been identified and studied as a promising alternative lixiviant for gold in acidic solutions. Eh-pH and ion species distribution diagrams for SCN-H2O, Au-SCN-H2O, Ag-SCN-H2O, Cu-SCN-H2O, and Fe-SCN-H2O systems were constructed to predict the behavior of each metal ion in the thiocyanate system and also to explain the experimental results. Thermodynamic analyses suggest that gold can be leached by thiocyanate under appropriate leaching potentials, forming aurous or auric complexes with thiocyanate, depending on the thiocyanate concentration and leaching potential. According to species distribution diagrams, silver (I) and copper (I) form insoluble salts at moderate thiocyanate concentrations and are soluble at low and high thiocyanate concentrations. Ferric ion forms a series of complexes with thiocyanate. The study of the ferric ion effect indicates that gold can be leached in acid thiocyanate solution with ferric sulfate as the oxidant. Also the presence of excess ferric ion reduces the apparent thiocyanate activity for copper (I) and silver (I) dissolution. The findings of this thermodynamic assessment are useful in the analysis of some of the phenomena encountered in the leaching and recovery of gold from thiocyanate solutions as discussed in subsequent papers.

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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 solid state formation of copper(I) coordination polymers by thermal reduction of copper(II) precursor compounds: Structure and reactivity of [Cu(NCS)2(pyrimidine)2]n

Reaction of copper(II) thiocyanate with pyrimidine leads to the formation of the new ligand-rich 1:2 (1:2 = ratio metal salt to ligand) copper(II) compound [Cu(NCS)2(pyrimidine)2]n (1). Its crystal structure was determined by X-ray single crystal investigations. It consists of linear polymeric chains, in which the Cu2+ cations are mu-1,3 bridged by the thiocyanato anions. The pyrimidine ligands are terminal N-bonded to the Cu2+ cations, which are overall octahedrally coordinated by two pyrimidine ligands and two N-bonded as well as two S-bonded thiocyanato anions. Magnetic measurements were preformed yielding weak net ferromagnetic interactions between adjacent Cu2+ centers mediated by the long Cu-S distances and/or interchain effects. On heating compound 1 to approx. 160 C, two thirds of the ligands are discharged, leading to a new intermediate compound, which was identified as the ligand-deficient 2:1 copper(I) compound [(CuNCS)2(pyrimidine)]n by X-ray powder diffraction. Consequently, copper(II) was reduced in situ to copper(I) on heating, forming polythiocyanogen as byproduct. Elemental analysis and infrared spectroscopic investigations confirm this reaction pathway. Further investigations on other ligand-rich copper(II) thiocyanato compounds clearly show that this in situ thermal solid state reduction works in general. The Royal Society of Chemistry 2009.

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