
%0 Journal Article
%A Nichols, PJ 
%A Grant, MW 
%T The Oxidation of Dithiocarbamate Anion by Substitution Inert Metal Complexes
%J Australian Journal of Chemistry
%D 1989/07/01
%V 42
%N 7
%P 1085-1101
%K 
%R https://doi.org/10.1071/CH9891085
%U https://www.publish.csiro.au/paper/CH9891085 
%X The kinetics of oxidation of dithiocarbamate anions to thiuram disulfides in aqueous acetone by {Fe(CN)6}3- and 11 other substitution inert metal complexes have been investigated. Outer-sphere electron transfer, resulting in the formation of dithiocarbamate thio radicals, is the rate determining step. A Marcus cross reaction treatment allows an estimate for the redox potential for the dithiocarbamate radical/anion couple. For diethyldithiocarbamate, E º(edtc/edtc-) = 425 ± 33 mV v.s.c.e. and the outer-sphere electron self-exchange rate constant is log kex = 7.0 ± 0.3. A comparison with thiophenolate oxidation is also given. 
