Copper halide

Copper electrodes Copper foil Copper fungicides Copper glycinate Copper-gold Copper halide Copper halide system... 

In 1968 the Monsanto Company announced the availability of novel soluble low molecular weight polyphenylene resins. These may be used to impregnate asbestos or carbon fibre and then cross-linked to produce heat-resistant laminates. The basic patent (BP 1037111) indicates that these resins are prepared by heating aromatic sulphonyl halides (e.g. benzene-1,3-disulphonyl dichloride) with aromatic compounds having replaceable nuclear hydrogen (e.g. bisphenoxy-benzenes, sexiphenyl and diphenyl ether). Copper halides are effective catalysts. The molecular weight is limited initially by a deficiency in one component. This is added later with further catalyst to cure the polymer. 

The Bergmann variation of the Balz Schiemann reaction is a two-step process featuring copper- or copper halide-catalyzed decomposition of aqueous or acetone solutions of arenediazonium fluoroborates containing alkyl or halogen substituents [30] A recent modification is a one-step technique featuring simultaneous diazoti-zation and decomposition by addition of aqueous sodium nitrite at 25 °C to a mixture of fluorobonc acid, copper powder, and 2 isopropyl 6 methylaniline to give 2-isopropyl-6 methylfluorobenzene in 73% yield [37]... 

Dithiocarbamate complexes of copper have been sythesized at a high rate. Reports of new complexes include the morpholine-4- (44), thio-morpholine, AT-methylpiperazine-4-, and piperidine- (291) dithiocarba-mates. Novel, polymeric complexes of the type Cu(pipdtc)2 (CuBr) in = 4, or 6) and Cu(pipdtc)2 (CuCl)4 have been prepared by reactions of[Cu(pipdtc)2] with the respective copper halide in CHCla-EtOH (418). The crystal structures of the polymers are known to consist of sheets of individual [Cu(pipdtc)2] molecules linked to polymeric CuBr chains via Cu-S bonds. A series of copper(I) dtc complexes have been the subject of a Cu and Cu NQR-spectral study (440). 

The ionic conductivity is much higher than in the corresponding copper halides (see Fig. 5). At temperatures above 250°C, they enter the region of optimized ionic conductors (150). 

The reaction on unactivated halides can also be done with copper halide catalysts (the Hurtley reaction), and with palladium complex catalysts. 

The stoichiometric reaction of organolithium or Grignard reagents with copper halides allows direct formation of organocopper species(103). 

Similarly to the alkyl derivatives, the most common route for arylcopper compounds is the reaction of a copper halide and aryllithium compounds (Equation (4)). Organocuprates with aryl groups are obtained by using an appropriate excess of the lithium reagent. Magnesium aryls have also been employed in transmetallation reactions with Cu(l) salts to yield both arylcopper compounds and arylcuprates (Equations (5) and (6)). 

Substituted terpyridine, 4,4, 4"-tris(5-nonyl)-2,2 <5, 2"-terpyridine (tNtpy), is a planar tridentate ligand that was successfully used in homogeneous ATRP of methyl acrylate and styrene [79]. Polymerization of both monomers was controlled and the resulting polymers had relatively low polydispersities (MJMn < 1.2). Similarly to PMDETA, the typical ligand to copper halide ratio used in the polymerization was 1 1. Terpyridine and its derivatives are expected to form tetra-coordinated complexes with copper in which the fourth coordination sphere is occupied by a monodentate ligand (Br-, Cl , solvent, monomer, etc.). Although,... 

Fig. 13. The temperature dependence of the precessional amplitudes (left) and relaxation rates (right) of the muonium centers observed in the copper halides. The open and filled triangles or squares are for Mu7 and Mu77 respectively. Note the similarity of the Cul data to that for Mu7 in CuCl and CuBr, suggesting that a transition to another center occurs in Cul but that the product has not been observed. From Kiefl et al. (1986b).

Axelrad, G., Laosooksathit, S., and Engel, R., Reactions of copper halide complexes of trivalent phosphorus with vinylic halides, /. Org. Chem., 46, 5200, 1981. 

Commercially useful materials require that the rate of the combined reaction is rapid. If the darkening takes place too slowly, or if the subsequent fading of the color is too slow, the materials will not be useful. The presence of the copper halide is essential in ensuring that the kinetics of the reaction are appropriate and that the process is reversible. 

It is important to mention the pioneering work of Reppe and co-workers who discovered as early as 1938 the industrial preparation of acrylic acid by car-bonylation of acetylene [28]. The reaction was conducted at 200-230 °C and 100 bar of CO and catalyzed by Ni(CO)4 in the presence of a copper halide. Selectivity of 90 and 85% were reached in acrylic acid with regard to acetylene and carbon monoxide, respectively [29]. 

More recently, several arylcopper compound syntheses that make use of a soluble form of a copper halide precursor, CuBr-DMS (DMS = dimethylsulfide) in DMS as the solvent have been reported. Some of these compounds, such as [Cu4(QH5)4(DMS)2] [61] and [Cu4(C6H4Me-2)4(DMS)2] [62], appeared to be DMS adducts and were fully characterized by X-ray crystal structure determination (see Fig. 1.7). It is interesting to note that these structures contain two- and three-coordinate copper atoms in trans positions. These structures may be envisaged as ion-pairs comprising Cu(Aryl)2 anions bound to Cu(DMS) cations through the Cipso atoms. 

Fig. 6 Representation of the metal and phosphorus environments in copper halide complexes with a Tyh/yhbridging bis-triphenylphosphonio-benzophospholide. The unsym-metric bridging mode is exemplified by the different P-Cu distances (in pm, data from [45] (a) and [53] (b))...

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