Abstract
The kinetics of the oxidation of copper(I) perchlorate with thiuram disulfide (tds) in acetonitrile and its mixtures with benzene or ethyl bromide have been investigated. It has been shown that the rate of the reaction is limited by the inner-sphere transfer of an electron from the copper(I) ion to tds in a complex of the type [CuI(tds)]+. The subsequent dissociation of the anionradical tds —proceeds rapidly and leads to the formation of copper(II) dithiocarbamate which is recorded in the absorption spectra and by EPR. The rate constant of electron transfer has been determined (3·10−4sec−1) and it was found that it is practically independent of the polarity of the medium. The absence of such a correlation is attributed to the negligible energies of reorganization of the solvent in the inner-sphere electron transfer.
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