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The role of short-range diffusion in solvent-assisted mechanochemical synthesis of metal complexes

The role of short-range diffusion in solvent-assisted mechanochemical synthesis is demonstrated in studies of a polymorphic transition and a ligand dissociation reaction involving copper(i) thiocyanate complexes. The Royal Society of Chemistry.

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

 

Discovery of Cuprous thiocyanate

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Synthesis and structural characterization of five copper(I) complexes of[2,3-f]-pyrazino-[1,10]phenanthroline-2,3-dicarbonitrile and triphenylp hosphine

Five new copper(I) complexes containing PPh3 and C 16H6N6, [Cu(PPh3)(C 16H6N6)Cl]?H2O (1), [Cu(PPh3)(C16H6N6)Br]?CH 3CN (2),[Cu(PPh3)(C16H6N 6)I]? CH3CN (3), [Cu(PPh3)(C 16H6N6)(CN)]?0.5 CH2Cl 2 (4) and Cu(PPh3)(C16H6N 6)(SCN) (5) {PPh3 = triphenylphosphine, C 16H6N6 = [2,3-f]-pyrazino-[1,10] phenanthroline-2,3-dicarbonitrile} have been synthesized for the first time. These complexes are obtained by the reactions of CuX (X = Cl, Br, I, CN, SCN) with the bidentate ligand C16H6N6 and the monodentate ligand PPh3 in the molar ratio of 1:1:1 in the mixed solvent of CH2Cl2 and CH3CN(5 ml/5 ml). They are characterized by X-ray crystallography, luminescence, IR, 1H NMR and 31P NMR. In solid state the complexes 1-5 are mononuclear with similar structures, but in solution they have different structures according to their different 1H NMR signals. All the complexes exhibit intense luminescence in solid state at room temperature.

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

 

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2-Picolinic acid and benzoic acid from di-2-pyridyl ketone and acetophenone: A case of two copper catalysed Baeyer-Villiger rearrangements?

The synthesis and crystal structure elucidation of two novel polymeric copper(II) complexes has led us to propose a mechanism for the formation of 2-picolinic acid (pic) from di-2-pyridyl ketone (dpk) and benzoic acid from acetophenone. During studies into the interaction of copper ions with the dpk-acetophenone system, two complexes Na2(NCS)2(H 2O)[Cu(pic)2] (1) and Na2(H2O) 2[Cu(pic)2(NCS)2] (2) which contain pic coordinated to copper were isolated. The occurrence of (1) and (2) has led us to consider the Baeyer-Villiger rearrangement as a possible mechanism for the formation of (1) and (2).

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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 Cu(I) thiocyanate complexes with N-allylquinolinium: Synthesis and crystal structures of [C9H7NC3H 5]Cu(SCN)2 and [C9H7NC 3H5]Cu2(SCN)3

The crystals of [C9H7NC3H 5]Cu(SCN)2 (I) and [C9H7NC 3H5]Cu2(SCN)3 (II) were obtained in the reaction of N-allylquinolinium bromide with CuSCN and NH4SCN in a methanol solution. The crystals of I are triclinic: space group P1, Z = 2, a = 8.619(2), b = 8.755(2), c = 10.463(3) A, alpha = 77.18(3), beta = 69.95(3), gamma = 79.38(3), V = 718.1(3) A3. The crystals of II are opthorhombic: space group P212 121, Z = 4, a = 5.744(2), b = 16.799(4), c = 17.980(5), V = 1735.9(9) A3. The structure of compound I is built of infinite linear {Cu(SCN)2-}? anions and the N-allylquinolinium cations bonded additionally by relatively weak hydrogen contacts C-H…S. The [C9H7NC3H 5]+ cations are located between the corrugated layers of the {Cu2(SCN)3-}? anions in compound II. As in the case of the previously studied copper(I) halide complexes, the C=C bond of the allyl group in the N-allylquinolinium cation of complexes I, II does not interact with Cu(I).

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

 

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ANTIMICROBIAL COMPOSITIONS FOR USE IN PRODUCTS FOR PETROLEUM EXTRACTION, PERSONAL CARE, WOUND CARE AND OTHER APPLICATIONS

Compositions having antimicrobial activity contain surface functionalized particles comprising an inorganic copper salt which has low water solubility. These types of inorganic salts may also be introduced in porous particles to yield antimicrobial compositions. The compositions may optionally comprise additional antimicrobial agents, salts with high water solubility, organic acids, salts of organic acids and their esters. The compositions may be added to various fluids used in the petroleum extraction industry, or used as coatings on components used in this industry. These antimicrobial, materials may be used for reducing both anaerobic and aerobic bacteria and are also useful for reducing corrosion of ferrous components caused by anaerobic bacteria. Although such compositions may be used for any antimicrobial application, and some of the other important uses of these compositions are in wound care, personal care and waste processing,.

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

 

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Synthesis, molecular structures and ESI-mass studies of copper(I) complexes with ligands incorporating N, S and P donor atoms

Equimolar reaction of copper(I) bromide with 2-thiouracil (tucH2) in acetonitrile-methanol formed a light yellow solid which on subsequent treatment with a mole of triphenyl phosphine (PPh3) in chloroform has yielded a sulfur-bridged dinuclear complex, [Cu2Br2(mu-S-tucH2)2(PPh3)2] 2CHCl3 1. A reaction of copper(I) bromide with two moles of 2,4-dithiouracil (dtucH2) in acetonitrile-methanol followed by addition of two moles of PPh3, designed to form [Cu(mu-S,S-dtuc)2(PPh3)4Cu] 2a, instead resulted in the formation of previously reported polymer, {CuBr(mu-S,S-dtucH2)(PPh3)}n 2. Reaction of copper(I) iodide with 2-thiouracil (tucH2) and PPh3 in 1:1:2 molar ratio (Cu:H2tuc:PPh3) as well as that of copper(I) thiocyanate with pyridine-2-thione (pySH) or pyrimidine-2-thione (pymSH) and PPh3 in similar ratio, yielded an iodo-bridged unsymmetrical dimer, [(PPh3)2(mu-I)2Cu(PPh3)] 3 and thiocyanate bridged symmetrical dimer, [(PPh3)2Cu(mu-N,S- SCN)2Cu(PPh3)2] 4, respectively. In both the latter reactions, thio-ligands which initially bind to Cu metal center, are de-ligated by PPh3 ligand. Crystal data: 1, P21/c: 173(2) K, monoclinic, a, 13.4900(6); b, 17.1639(5); c, 12.1860(5) A; beta, 111.807(5) a; R, 5.10%; 2, Pbca: 296(2) K, orthorhombic, a, 10.859(3); b, 17.718(4); c, 23.713(6) A; alpha=beta=gamma, 90 a; R, 4.60%; 3, P21: 173(2) K, monoclinic, a, 10.4208(7); b, 20.6402(12); c, 11.7260(7) A; beta, 105.601(7)a; R, 3.97%; 4, P-1: 173(2) K, triclinic, a, 10.2035(4); b, 13.0192(5); c, 13.3586(6) A; alpha, 114.856(4); beta, 92.872(4)a; gamma, 100.720(4)a; R, 3.71%. ESI-mass studies reveal different fragments of complexes.

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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 present application is directed to a coating composition comprising a ceramic binder and inorganic copper compound particles. Generally, the inorganic copper compound particles have a median particle size of less than 5 micrometers. In some embodiments, the particles have a median particle size of greater than 1 micrometer. The inorganic copper compound particles may be non-photocatalytic. The coating may also be placed on a structural layer.

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

 

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Treatment of an acetonitrile solution of CuI with 1,7-dithia-18-crown-6 (1,7-DT18C6) at 100C affords the coordination polymer ? 1[(CuI)2(1,7-DT18C6)2] (1) in which 1,7-DT18C6 ligands bridge (CuI)2 rings into double chains. 1D polymers of the type ?1[M{(Cu3I 4)(1,7-DT18C6)}] (M = K, 2; M = Cs, 3) can be isolated under similar conditions in the presence of respectively KI and CsI. Both contain bridging heptacyclic [Cu6I8]2- units but crystallise in different space groups, namely P1 and C2/m. The cesium cation of 3 is markedly displaced from the best plane through the thiacrown ether donor atoms. Reaction of 1,7-DT18C6 with CuSCN in the presence of NaSCN yields ?2[{Na(CH3CN)2} {(CuSCn) 2(1,7-DT18C6)}][Cu(SCN)2] (4), in which ?1[(CuSCN)2] double chains are linked through macrocycles into sheets. Infinite ? 1[{Cu(SCN)2}-] chains compensate the charge of the Na+ cations. Complex 1 can imbibe 0.90 mol CsNO3 per mol of 1,7-DT18C6 pairs.

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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(I) complexes of 1,2-bis(diphenylphosphino)ethane (dppe) with a stoichiometry Cu2(dppe)3(X)2 [X – = CN- (1), SCN- (2), NO3- (3)] are obtained from direct reactions of CuX and dppe. The complexes are structurally and spectroscopically (NMR and IR) characterized. The structure of the [Cu2(dppe)3]2+ dication is similar to the structural motif observed in many other complexes with a chelating dppe and a bridging dppe connecting two copper centers. In complexes 1-3, the anions are confined to the cavity formed by the phosphines which force a monodentate coordination mode despite the predominant bidentate/bridging character of the anions. The coordination angles rather than the thermochemical radii dictate the steric requirement of anions. While the solution behavior of 3, with nitrate, is similar to complexes studied earlier, complexes with pseudohalides exhibit new solution behavior.

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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 mask is provided that can inactivate viruses adhering thereto even in the presence of lipids and proteins regardless of whether or not the viruses have an envelope. The mask can inactivate viruses adhering thereto and includes a mask body provided with a member used when the mask is worn and virus inactivating fine particles having a virus inactivating ability and held by the mask body. The virus inactivating fine particles are particles of at least one selected from the group consisting of platinium(II) iodide, palladium(II) iodided, silver(I) iodide, copper(I) iodide, and copper(I) thiocyanate.

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