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

 

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Ullmann condensations of diarylamines with iodobenzenes has been investigated under homogeneous and a heterogeneous catalytic conditions with cupruos and cupric salts, as well as powered copper metal.Copper catalyzed condensation of diarylamines with iodoaromatics is relatively insensitive to substituent (for substituted iodobenzenes p=-0.25; for substituted diphenylamines p=1.09) but quite sensitive to halogen (k1/kBr.200).The first direct evidence for solution catalysis after filtration of a metal catalyzed reactions was obtained.Quantitative analysis of reaction rates, product yields, and catalyst characteristics leads to a comprehensive picture of the formation of soluble cuprous ions as the single active catalytic species under all conditions investigated.This hypothesis rationalizes many of the perplexing results which typify the literature associated with copper catalyzed nucleophilic aromatic substitution.

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

 

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A straightforward synthesis of the zwitterionic benzoquinonemonoimine 8 is reported. This molecule is a rare example of a zwitterion being more stable than its canonical forms. It is shown that 8 is best described as constituted of two chemically connected but electronically not conjugated 6 pi electron subunits. Its reactivity with electrophiles such as H+, CH3+, and metal salts leads to the synthesis of new 12 pi electron molecules 12 (H +), 14 (CH3+), and 20 (pd2+), respectively, in which one or both 6 pi electron subsystems localize into an alternation of single and double bonds, as established by X-ray diffraction. The acidity of the N-H protons of 8 can be modulated by an external reagent. Dependent on the electrophile used, the control of the pi system delocalization becomes possible. When the electrophile simply adds to the zwitterion as in 12, 14, or 15, there is no more negative charge to be delocalized and only the positive charge remains delocalized between the nitrogen atoms. Furthermore, when a reaction with the electrophilic reagent results in deprotonation, as in 17-21, there remains no charge in the system to be delocalized. DFT calculations were performed on models of 8, 12, 14, 20, and on other related zwitterions 9 and 10 in order to examine the influence of the fused cycles on the charge separation and on the singlet-triplet energy gap. An effect of the nitrogen substituents in 8 is to significantly stabilize the singlet state. The dipole moment of 8 was measured to be 9.7 D in dichloromethane, in agreement with calculated values. The new ligands and complexes described in this article constitute new classes of compounds relevant to many areas of chemistry.

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

 

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The addition of Yb(OTf)3 (10 mol%) in a Rh2(OAc)4-catalyzed reaction of o-(methoxycarbonyl)-alpha-diazoacetophe-none with N-methylmaleimide in CH2Cl2 or in diethyl ether gave cycloadducts with high endo-selectivity (endo:exo = 95:5-96:4). The CuOTf (20 mol%)-or CuCl-Yb(OTf)3 (5 mol%)-catalyzed reaction also gave 1,3-dipolar cycloadducts in an endo-selective manner (endo:exo = 94:6). On the other hand, a reaction using only Rh2(OAc)4 (5 mol%) as the catalyst in benzene under reflux gave cycloadducts with exo-selectivity (endo:exo = 11:89). The reaction of N-ethyland N-phenylmaleimides under the same conditions showed a similar tendency in terms of the 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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Simple copper(ii) hydroxide Cu(OH)2 could act as an efficient heterogeneous catalyst for selective oxidative cross-coupling of a broad range of terminal alkynes and amides using air as a sole oxidant, giving the corresponding ynamides in moderate to high yields (56-93% yields). The Royal Society of Chemistry 2012.

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

 

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(Graph Presented) Cu2ZnSnS4 (CZTS) is a promising new material for thin-film solar cells. Nanocrystal dispersions, or solar paints, present an opportunity to significantly reduce the production cost of photovoltaic devices. This communication demonstrates the colloidal synthesis of CZTS nanocrystals and their use in fabricating prototype solar cells with a power conversion efficiency of 0.23% under AM 1.5 illumination.

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

 

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

 

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

 

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

 

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The heat of combustion of a copper complex with 2,7,12,17-tetramethyl-3,8,13,18-tetraethylporphine was measured in an isothermal liquid calorimeter with a stationary calorimetric bomb. The standard enthalpies of combustion and formation of the complex studied were calculated (DeltacH =-21694.77 ± 12.54 kJ/mol, DeltafH = 3796.59 ± 12.60 kJ/mol).

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