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Kinetics and mechanism of the reaction of benzyl bromide with copper in hexamethylphosphoramide
Author(s) -
Egorov Anatoly M.,
Matyukhova Svetlana A.,
Anisimov Alexander V.
Publication year - 2005
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20065
Subject(s) - chemistry , hexamethylphosphoramide , copper , benzyl bromide , substituent , bromide , reaction mechanism , reaction rate constant , kinetics , hammett equation , inorganic chemistry , medicinal chemistry , dissolution , photochemistry , organic chemistry , catalysis , physics , quantum mechanics
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. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 296–305, 2005