Copper, tetra

The complexation of anionic species by tetra-bridged phosphorylated cavitands concerns mainly the work of Puddephatt et al. who described the selective complexation of halides by the tetra-copper and tetra-silver complexes of 2 (see Scheme 17). The complexes are size selective hosts for halide anions and it was demonstrated that in the copper complex, iodide is preferred over chloride. Iodide is large enough to bridge the four copper atoms but chloride is too small and can coordinate only to three of them to form the [2-Cu4(yU-Cl)4(yU3-Cl)] complex so that in a mixed iodide-chloride complex, iodide is preferentially encapsulated inside the cavity. In the [2-Ag4(//-Cl)4(yU4-Cl)] silver complex, the larger size of the Ag(I) atom allowed the inner chloride atom to bind with the four silver atoms. The X-ray crystal structure of the complexes revealed that one Y halide ion is encapsulated in the center of the cavity and bound to 3 copper atoms in [2-Cu4(//-Cl)4(//3-Cl)] (Y=C1) [45] or to 4 copper atoms in [2-Cu4(/U-Cl)4(/U4-I)] (Y=I) and to 4 silver atoms in [2-Ag4(/i-Cl)4(/i4-Cl)] [47]. NMR studies in solution of the inclusion process showed that multiple coordination types take place in the supramolecular complexes. 

Baxter PNW, Lehn J-M, Kneisel BO, Fenske D (1997) Self-assembly of a symmetric tetra-copper box-grid with guest trapping in the solid state. Chem Commun 2231-2232... 

Fig. 3 X-ray crystal structures of a the tetra-copper assembly [Cu4(pprd)4(C2H4)4](PF6)4 (11) and b the tri-copper assembly [Cu3(pprd)3(C2H4)3](C104)3 3 (12)...

It has been found as the anionic array of trigonal Cu(I) coordinated by cyanide ions in bis(tctrabutylammoniiim)hexakis(iT-cyano)-tetra-copper(l), see Figure 6.36 f38]. 

Figure 6.36 The noe net in bis(tetrabutylaminoniuni)hexakis r -cyano)-tetra-copper(I) [381- A seven ring is emphasised.

C3 2H3 8Ag2Cu 02 8 f Silver(I) di-M3 hydroxo-tetrakis-M phthalato-tetra-copper(II) decahydrate, 45B, 1126... 

Ci2Hii,CUi,Ii,N2, Bis(M iodo)-bis(M3 iodo)-bis(2-methylpyridine)tetra-copper(l), 46B, 1064... 

Extending this line of thought, Puddephatt s group reported in 1993 cavitands bridged with P(III) moieties. They demonstrated the formation of several tetra-gold (I) and tetra-copper(I) complexes and showed that they were capable of the size-selective binding of halide ions [197]. Molecular mechanics and NMR data were consistent with the stereochemistry of the free ligand in which the lone pairs on the phosphorus point towards the center of the pocket (60). 

Brynda E, Kalvoda L, Koropeoky I, Nespurek S and Rakusan J 1990 Copper tetra-4-tert-butylphthaloeyanine Langmuir-Blodgett-films—photoeleetrioal and struotural studies Synth. Met 37 327-33... 

When naming complex ions the number and type of ligands is written first, followed by the name of the central metal ion. If the complex as a whole has a positive charge, i.e. a cation, the name of the central metal is written unchanged and followed by the oxidation state of the metal in brackets, for example [Cu(N 113)4] becomes tetra-ammine copper(II). A similar procedure is followed for anions but the suffix -ate is added to the central metal ion some examples are ... 

Trimethylene dibromide (Section 111,35) is easily prepared from commercial trimethj lene glycol, whilst hexamethylene dibromide (1 O dibromohexane) is obtained by the red P - Br reaction upon the glycol 1 6-hexanediol is prepared by the reduction of diethyl adipate (sodium and alcohol lithium aluminium hydride or copper-chromium oxide and hydrogen under pressure). Penta-methylene dibromide (1 5-dibromopentane) is readily produced by the red P-Brj method from the commercially available 1 5 pentanediol or tetra-hydropyran (Section 111,37). Pentamethylene dibromide is also formed by the action of phosphorus pentabromide upon benzoyl piperidine (I) (from benzoyl chloride and piperidine) ... 

Brom-jod, n. iodine bromide, -kalium, n. potassium bromide, -kalzium, n., kalk, tn. calcium bromide, -kampher, tn. bromo-camphor, Pharm.) monobromated camphor, -kohlenstoff, tn. carbon (tetra)bromide. -korper, tn. Colloids) "bromide body (bromide ion), -kupfer, n. copper bromide, lauge, /. bromine lye (solution of sodium hypobromite and bromide made by passing bromine into sodium hydroxide solution), -lithium, n. lithium bromide. -Idsung, /. bro-nune solution, -magnesium, n. magnesium bromide. -metall, n. metallic bromide. 

A solution of CuCl, 2H20 (6.2 g, 22 mmol) in DMF (62 mL) was added to l,l9-dideoxy-2.8.12,18-tetra-ethyl-1,3.7,13,17,19-hexamethylbiladiene-ucdihydrobromide (1.2 g, 1.82 mmol) and the mixture was heated under reflux for 2 min. After cooling, the crystalline product was collected by filtration, washed with H20 and MeOH and extracted in a Soxhlet apparatus with CHC13. The extract was reduced to a volume of about 10 mL, and hot MeOH was added. Copper etioporphyrin II (13a) crystallized as red plates yield 598 mg (61 %). 

A second reaction which is very often used for the preparation of phthalonitriles, although the yields are usually not reproducible, is the Rosenmund-von Braun reaction (see Houben-Weyl, Vol. E5, p 1460).106 107 Herein, a benzene derivative with a 1,2-dibromidc or 1,2-dich-loride unit is treated with copper(I) cyanide in dimethylformamidc or pyridine. During this reaction the formation of the respective copper phthalocyanine often occurs. This can be used as an easy procedure for the exclusive synthesis of copper phthalocyanines (see Section 2.1.1.7.),1 os-109 but can also lead to problems if the phthalonitrile is required as the product. For example, if l,2-dibromo-4-trifluoromethyl-benzene is subjected to a Rosenmund-von Braun reaction no 4-trifluoromethylphthalonitrile but only copper tetra(tri-fluoromethyljphthalocyanine is isolated.110... 

Copper(II) 2 3,9 10,16 17,23 24-Tetra(7-aza-15-crown-5)phthalocyanine (4h) Typical Procedure 108... 

Method B A mixture of copper(II) phthalocyanine (3 1.2 g, 2 mmol) and C1S03H (5 mL) was stirred for 3 h at 138-140 C and then for 3 h with SOCI, (1.5 mL) at 80 85 C. The mixture was then cooled, poured onto ice, and filtered. The precipitate was washed on the filter with cold H,0 until neutral, pressed off well, and dried. The l,4-tetra(chlorosulfonyl)phthalocyanine 4 obtained was mixed with Et2NH (2mL) in CHCl3 (50 mL)and the mixture was stirred for 24 hat 25 30 C. By repeated chromatographic separation (alumina, CHC13/ benzene 2 1) the title compound 5 was isolated yield 0.3 g (13 %). 

Mono-, bi-, tetra- and poly-nuclear copper(II) halogenocarboxylates. M. Melnik, Coord. Chem. Rev., 1981,36,1 14 (167). 

Pentafluorophenylcopper tetramer Copper, tetrakis(pentafluoro-phenyl)tetra- (8,9) (34077-61-7)... 

The effect of bath additives on the electrocodeposition of alumina-copper has been studied. Chloride ion was found to significantly inhibit incorporation of alpha alumina in an acidic copper bath [27, 51], whereas thallium ions, cesium ions, and tetra-ethylene pentamine were promoters [25, 32]. 

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