The reaction of copper with benzyl bromides in hexamethylphosphoramide has been studied. The kinetic and thermodynamic parameters of the reaction have been obtained. Hammett plots of log (k/k o ) vs the substituent constant σ gave good correlations (ρ = 0.15, S ρ = 0.02, r = 0.954). The structure of the organic group has little effect on the rate of reaction of benzyl bromide with copper. In the absence of atmospheric oxygen, the oxidative dissolution of copper occurred by the mechanism of single-electron transfer with the formation of 1,2-diphenylethane and copper(I) complexes. The stereochemistry and intermediates compound was also investigated.The reaction mechanism is discussed. C 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: [296][297][298][299][300][301][302][303][304][305] 2005

The reaction of copper with benzyl chlorides in dipolar aprotic solvents has been investigated. The kinetic and thermodynamic parameters of the reaction of copper with benzyl chloride in dimethyl sulfoxide, dimethylacetamide, and hexamethylphosphoramide have been obtained. Hammett plots of log (k/k • ) versus the substituent constant σ gave good correlation. The structure of the organic group has little effect on the rate of reaction of benzyl chloride with copper. The kinetic and thermodynamic parameters were correlated with donor number of solvent (DN SbCl 5 ). The ratio k RBr /k RCl and Hammett ρ values provide evidence in favor of the halogen atom transfer mechanism.

Reaction of copper(0) with carbon tetrachloride in DMF was studied. In the absence of atmospheric oxygen, the oxidative dissolution of copper(0) occurs as one-electron transfer and gives rise to C 2 Cl 2 and copper(I) complexes. Kinetic and thermodynamic parameters of the process are determined, and its mechanism was considered.

The reaction of copper metal with various substituted benzyl bromides in dimethylformamide has been studied and the kinetic and thermodynamic parameters of the reaction have been obtained. Hammett plots of log(k/k • ) vs the substituent constant σ gave good correlations (ρ = 0.24, S ρ = 0.03, r = 0.951). The structure of the organic group has little effect on the rate of reaction of substituted benzyl bromides with copper. In the absence of atmospheric oxygen, oxidative dissolution of copper occurred by the mechanism of single-electron transfer with the formation of 1,2-diphenylethanes and copper(I) complexes. The stereochemistry and intermediate compound were also studied and the reaction mechanism is discussed.

The reaction of copper with benzyl bromides in dipolar aprotic solvents has been studied. There are no linear or other simple relations between ε, 1/ε, Y, P, n