Cupric Halides Research Articles

The absorption of cupric halides

Thin films of cupric halides were prepared and their absorption was measured in 185–3,500 nm spectral region. The interpretation of the absorption curves is given on the basis of electrond-d and charge transfer transitions in the prolonged octahedral halogenocupric complexes.

Reactions of cupric halides with organic compounds—VII : Reactions of 9-alkoxy- and 9-acyloxy-10-alkylanthracenes

9-Alkoxy(or acyloxy)-10-methylanthracenes undergo reaction with cupric halides at the Me group to give coupled products, whereas 9-alkoxy(or acyloxy)-10-benzyl(or ethyl)anthracenes react at the alkoxy or acyloxy group to afford 10-benzyl- and 10-ethylideneanthrones respectively. Both types of reaction are postulated to proceed by a radical mechanism. 9-Benzyl- and 9-methyl-10-phenoxyanthracenes behave differently giving on reaction with cupric chloride 9-chloro-10-phenoxyanthracene as a result of a ligand-transfer reaction.

Reactions of cupric halides with organic compounds—VIII : Reactions of 9-acylanthracenes

9-Acylanthracenes undergo reaction with cupric halides in chlorobenzene to give 9-acyl-10-halogenoanthracenes together with 9-halogeno- and 9,10-dihalogenoanthracenes. The products arise from ligand-transfer reactions of the cupric halide and the 9-acylanthracene at the 9- and 10-positions. 9-Acetylanthracene gives 9-bromoacetylanthracene on reaction with cupric bromide in ethyl acetate-chloroform.

Borono and halo derivatives of tricarbonylcyclopentadienylmanganese and -rhenium

1. By the action of tributyl borate on tricarbonyl(lithiocyclopentadienyl)manganese and -rhenium the corresponding boronic acids were prepared. 2. Some properties of these acids were studied. In an aqueous medium they are readily hydrolyzed with formation, respectively, of tricarbonylcyclopentadienylmanganese (TCM) and tricarbonyicyclopentadienylrhenium (TCR), and under given conditions the rate of hydrolysis of TCR-boronic acid is higher than the rate of hydrolysis of TCM-boronic acid. 3. The chloro and bromo derivatives of TCR and the already-known similar derivatives of TCM were prepared by the action of cupric halides on symmetrical mercury derivatives of TCM and TCR. 4. Bromo derivatives of TCM and TCR are inert in nucleophilic exchange reactions of halogen.

Reactions of cupric halides with organic compounds—IV : Reactions of 9-alkoxy- and 9-acyloxyanthracenes

9-Alkoxy and 9-acyloxyanthracenes react with cupric bromide and with cupric chloride to give 9-alkoxy (or acyloxy) 10-halogenoanthracenes and/or bianthron-9-yl. The formation of the former product proceeds by ligand transfer of halogen of the cupric halide whilst bianthron-9-yl results from the dimerization of 9-anthryloxy radicals. These are formed in a 4-centre transition state between the substituted anthracene and the cupric halide. The ratio of the two products and the relative rates of reaction are interpreted in terms of the above processes. The reaction of 9-methylthioanthracene with cupric halides was also studied.

Reactions of cupric halides with organic compounds—III : 9-Alkyl and 9-arylanthracenes

9-Alkyl and 9-arylanthracenes have been shown to undergo halogenation with cupric halides to give good yields of their 10-halogenated derivatives. Electron-donating groups in 9-arylanthracenes were shown to increase the rate of reaction. The results are interpreted in terms of a ligand-transfer mechanism.

Reactions of cupric halides with organic compounds—V: Reactions of 9,10-dialkyl- and 9-alkyl-10-arylanthracenes

9-Aryl-10-methylanthracenes undergo reaction with cupric halides to give the corresponding 9-aryl-10-halogenomethylanthracenes. 9-Ethyl- and 9-benzyl-10-methylanthracenes similarly undergo reaction at the Me group rather than at the Et or Bz groups to form the halogenomethyl compound. These results indicate that the 9-alkyl-10-anthrylmethyl radical is more stable than the radicals which would be formed by hydrogen abstraction from the Et or Bz groups. These reactions also gave products in which alkyl groups were replaced by halogen. A mechanistic interpretation of these results is advanced. The reactions of 9-alkyl (or aryl) 10-methylanthracenes with N-bromosuccinimide were also examined.

The preparation, properties, and infra-red spectra (4000-170 cm −1) of dialkylamine complexes of cupric halides

The interaction between secondary aliphatic amines, R 2NH ( R = Et, Pr n , Pr i , Bu n , Bu i , Bu s , n-hexyl, 2-ethylhexyl, cyclohexyl, benzyl, allyl; or R 2 NH = pyrrolidine) and cupric bromide and/or chloride is described. All the bases afforded 2:1 adducts except those amines branched in the α-position (i.e. R = Pr i , Bu s , cyclohexyl), with which aminolysis and oxidation-reduction occurred. Pyrrolidine with cupric chloride afforded a 3:1 adduct, the formation of which is ascribed to the small steric requirements of this amine. Thermal decomposition of the bis(amine) complexes resulted in the evolution of the parent secondary amine and formation of diamagnetic materials of indeterminate composition, but containing the dialkylammonium grouping. Infra-red (4000-170 cm −1) spectroscopic and magnetic data are presented.

Reaction of cupric halides with organic compounds—II : 9-Halogenoanthracenes

9-Bromoanthracene and 9-chloroanthracene with cupric chloride and cupric bromide respectively give only 9-bromo-10-chloroanthracene. The reaction is postulated to proceed by a radical mechanism. Reactions of 9-halogenoanthracene with other halogenating agents were also examined.

The far-infrared spectra (450-80 cm −1) of some complexes formed by semicarbazide, thiosemicarbazide, acetone semicarbazone, and 1,2,4-triazole with cupric halides and oxyacid salts

The far-infrared spectra (450-80 cm −1) of a number of complexes of the type CuL 2X 2 and CuLX 2 [L = semicarbazide (sc), thiosemicarbazide (tsc), acetone semicarbazone (scac), or 1,2,4-triazole (trz); X  Cl, Br, NO 3, ClO 4, or 1 2 SO 4] have been studied in the solid state. The absence of copper—halogen bond stretching absorptions in the spectra of CuL 2Cl 2 and CuL 2Br 2 (L = sc, tsc, scac) is readily interpreted in terms of a high degree of tetragonal distortion along the halogen—copper—halogen axes. However, in the compounds CuLCl 2 and CuLBr 2 (L = sc, tsc, trz) studied, copper—halogen stretching vibrations have been identified; structures are suggested from consideration of the observed ν(CuX) and ν(CuL) modes. The compounds Cusc 2(NO 3) 2, Cusc 2(ClO 4) 2, and Cutsc 2(SO 4) appear to contain coordinated or “semi-co-ordinated” oxyanions, but Cuscac 2(NO 3) 2 does not; with Cutsc 2(NO 3) 2 and Cutsc 2(ClO 4) 2 the situation is less certain. Assignments of gn(CuL), ν(Cu-halogen), and ν(Cu-oxyanion) modes are tabulated and discussed in terms of co-ordination number, geometry and bonding. Comparisons with results of mid-infrared and electronic spectral data are made.

Magnetic Moments and d–d Bands of N-n-Propanolsalicylaldiminato-copper(II)

Abstract The reaction of cupric acetate with the reaction mixture of γ-aminopropyl alcohol and substituted salicylaldehydes in ethanol gave dimeric copper(II) complexes. The postulated structure of these complexes makes it possible to test the substituent effect transmitted to the coordinating atoms which are not in the superexchange pathway between copper-(II) ions in a pair. The magnetic moments observed at room temperature were corrected for the temperature variations to those at 25°C by graphic method based on Bleaney and Bowers’ equation. The observed substituent effect on the relation between μeff25°C and λmax is different from that observed for dimeric cupric halides complexes of substituted pyridine N-oxides. In these complexes the substituent effect transmits to the bridging oxygen atom in the superexchange pathway. As compared with the parent complex (H), methyl, chloro and benzo groups weakened the magnetic interaction but nitro group strengthened it. An interpretation of the substituent effect is given based on the idea of the mutual influences on the coordinate bonds.

The far-infra-red spectra and structure of the bis(4-methylpyridine) complexes of cupric halides

The far-infra-red spectra and structure of the bis(4-methylpyridine) complexes of cupric halides

Reactions of hydrazones and azines with metal salts

In the reaction between the azines of acetaldehyde, acetone, butanone, and cyclohexanone and cupric chloride, bromide, and acetate in water complexes were formed of the azines with cuprous halides of composition $$\left( {\begin{array}{*{20}c} R \\ {R_1 } \\ \end{array} \begin{array}{*{20}c} \setminus \\ / \\ \end{array} C = N - N = C\begin{array}{*{20}c} / \\ \setminus \\ \end{array} \begin{array}{*{20}c} R \\ {R_1 } \\ \end{array} } \right) \cdot nCuX,$$ in which X=Cl, Br, or I and n=2 or 3. These are analogous to the complexes prepared by us earlier from hydrazones and cupric halides.

Communications-Halogenation of Unsaturated Aldehydes with Cupric Halides

Communications-Halogenation of Unsaturated Aldehydes with Cupric Halides

The Composition of the Nitric Oxide Complexes of Cupric Halides1

The Composition of the Nitric Oxide Complexes of Cupric Halides¹