Copper, tris salts

Partial hydrolysis of a potentially heptadentate Schiff-base tripodal ligand derived from tris-(2-aminoethyl)amine and 2-hydroxyacetophenone, induced by copper(II) salts, was reported and the final copper(II) complex (377) was characterized.333 Using salicylaldehyde as a co-ligand, with a copper(II) complex (378), catalytic epoxidation was demonstrated 334... 

Monomeric copper(I) tris(carbene) complexes were prepared by reacting with copper(I) salts. The X-ray structures... 

Deposition of copper metal Since Cu(II) is the preferred oxidation state of copper, Cu2+ salts are more stable and more available, hence, in a technical application it would be favorable to use them as starting material. We tried to reduce Cu(CF3S03)2 dissolved in [EMIM][TfO], [BMP][TfO] and [BMIM][TfO] with an argon plasma (gas pressure 100 Pa) as well as with a nitrogen plasma (100 Pa), respectively. Additional experiments with Cu(CF3SC>3)2 dissolved in [EMIM][TfO] and Ar/H2 plasmas were carried out, with the distance between the hollow cathode in the gas phase and the surface of the ionic liquid metal salt solution being 3, 45 and 100 mm. Moreover, for the 3 mm distance several experiments with different gas pressures from 50 to 500 Pa were carried out. 

Reduction of acid chlorides to aldehydes One of the most useful synthetic transformations in organic synthesis is the conversion of an acid chloride to the corresponding aldehyde without over-reduction to the alcohol. Until recently, this type of selective reduction was difficult to accomplish and was most frequently effected by catalytic hydrogenation (the Rosenmund reduction section 6.4.1). However, in the past few years, several novel reducing agents have been developed to accomplish the desired transformation. Among the reagents that are available for the partial reduction of acyl chlorides to aldehydes are bis(triphenylphosphine)cuprous borohydride , sodium or lithium tri-terf-butoxyaluminium hydride, complex copper cyanotrihydridoborate salts °, anionic iron carbonyl complexes and tri-n-butyltin hydride in the presence of tetrakis(triphenylphosphine)palladium(0). ... 

There also exists a considerable number of ionic tris(thiourea) complexes. Thiourea is capable of reducing copper(II) salts to copper(I) complexes in acid solution to form [Cu(thiourea)3] salts. The following have been isolated chloride (194, 195), nitrate (194), oxalate (194, 195, 298), monohydrogen arsenate, and phosphate (298). 

Tris-(2-imidazolidinethione)copper(I) acetate and sulfate have similarly been obtained by reducing the appropriate copper(II) salt with the ligand in water. They are presumably ionic since solutions of the latter gave an immediate precipitate of BaS04 when treated with BaCl2 249). Tris (0-ethylaminothioformate)copper(l) chloride 101, 299) and bromide 299) have been prepared from the copper(I) salts. 

Carboxylic acids, a-bromination of, 55, 31 CARBOXYLIC ACID CHLORIDES, ketones from, 55,122 CARBYLAMINE REACTION, 55, 96 Ceric ammonium nitrate [Ammonium hexa-nitrocerate(IV)], 55,43 Chlorine, 55, 33, 35,63 CHROMIUM TRIOXIDE-PYRIDINE COMPLEX, preparation in situ, 55,84 Cinnamonitrile, a-phenyl- [2-Propeneni-trile, 2,3-diphenyl-], 55, 92 Copper(l) iodide, 55, 105, 123, 124 Copper(I) thiophenoxide [BenzenethioL copper(I) salt], 55, 123 CYCLIZATION, free radical, 55, 57 CYCLOBUTADIENE, 55,43 Cyclobutadienoiron tricarbonyl [Iron, tri-carbonyKp -1,3-cyclo-butadiene)-], 55,43... 

The pH-dependent NMR spectrum of [Ru(bipy)2(py)2] salts has been shown not to involve the formation of covalent hydrates. The reaction of 2,4,6-tris(2-pyridyl)-l,3,5-triazine (46) with aqueous copper(I) salts results in a metal-promoted hydrolysis to yield complexes of 2-pyridinecarboxamide and (47). A number of metal complexes have been characterized structurally from these reactions. 

Aryltrimethyl- or tri- -butylstaimanes as common Stille reagents are also successfully homo-coupled under palladium catalysed reactions in the presence of ethyl 2,3-dibromophenylpropionate (443) [26], or more conveniently by oxidation with copper(I) salts, e.g. CuCl [27], or copper(II) salts, e.g. Cu(N03)2 3H20 [28,29], which proceed smoothly at room temperature in tetrahydrofuran or DMF to afford symmetrical biaryls in excellent 3uelds. The Cu(N03)2-mediated homo-coupling works well also with diaryldimethyl(or -butyl)stannanes [30]. Moreover, the reaction can be accomplished with a catalytic amount of copper(II) chloride or manganese(II) bromide (10 mol%) in the presence of iodine as stoichiometric oxidant [31]. For example, compound 443, acting as an oxidant, converts the phenyltri-n-butylstannane (184) to biphenyl (8) in 86% yield [26], Scheme 11. 

Tri-t-butyl phosphine can be more effective in the coupling of reluctant aryl bromides (Scheme 2.118). Bulky electron-rich biaryl phosphine ligands, such as 2385, can also promote the Sonogashira reaction of difficult aryl chlorides (Scheme 2.119). ° Interestingly, in this case, the presence of copper(I) salts inhibited the reaction, and the copper-free version provided better yields. Aryl tosylates, easily prepared from phenols, also couple under these conditions (Scheme 2.120). 

Reaction of tra i-bis(tri-n-butylphosphine)diethynylnickel (34) with 1-alkynes in the presence of an amine complex of a copper(I) salt as a catalyst gives quantitatively alkynyl ligand exchange products. In this synthetic method, complex 34 reacts with appropriate a,cu-diethynyl compounds to afford high molecular weight... 

The same group also showed that tris(dithiocarbamate) complexes react with a range of copper(I) salts in acetonitrile giving 1 1, 2 1 and 3 1 heterobimetallic adducts together with polymeric species (Fig. 175), the latter being linked and cross-linked into a novel double-stranded polymer by centrosymmetric displaced step Culfi units (498,1400,1401). In contrast, reaction with [Cu(BF4)2] simply yields [Co2(S2CNR2)s][BF4] and [Cu(S2CNR2)2][BF4] (1118). 

Aryl bromides were also perfluoroethylated under these conditions [205] The key to improved yields was the azeotropic removal of water from the sodium perfluoroalkylcarboxylate [205] Partial success was achieved with sodium hepta-fluorobutyrate [204] Related work with halonaphthalene and anthracenes has been reported [206 207] The main limitation of this sodium perfluoroalkylcarboxylate methodology is the need for 2 to 4 equivalents of the salt to achieve reasonable yields A trifluoromethylcopper solution can be prepared by the reaction of bis(tri-fluoromethyl)mercury with copper powder in /V-methylpyrrolidone (NMP) at 140 °C [208] (equation 138) or by the reaction of N-trifluoromethyl-A-nitro-sotnfluoromethane sulfonamide with activated copper in dipolar aprotic solvents [209] This trifluoromethylcopper solution can be used to trifluoromethylate aro matic [209], benzylic [209], and heterocyclic halides [209]... 

Chemical analysis revealed that commercial food grade copper chlorophyllin is not a single, pure compound, but is a complex mixture of structurally distinct porphyrins, chlorin, and non-chlorin compounds with variable numbers of mono-, di-, and tri- carboxylic acid that may be present as either sodium or potassium salts. Although the composition of different chlorophyllin mixtures may vary, two compounds are commonly found in commercial chlorophyllin mixtures trisodium Cu (II) chlorin Cg and disodium Cu (II) chlorin which differ in the number of... 

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