
TY  - JOUR
A1  - Nichols, PJ 
A1  - Grant, MW 
T1  - The Oxidation of Dithiocarbamate Anion by Substitution Inert Metal Complexes
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1989
VL  - 42
IS  - 7
SP  - 1085
EP  - 1101
KW  - 
UR  - https://doi.org/10.1071/CH9891085 
N2  - 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. 
ER  -

