Journal of Physical Chemistry, Vol.100, No.35, 14823-14827, 1996
Mechanism of Dimerization of 1,4-Dithiafulvenes into TTF Vinylogues
Mechanism of the oxidative dimerization of DTF (dithiafulvenes) to form TTF vinylogues (tetrathiafulvalenes) has been investigated by cyclic voltammetry at low and high scan rates for a series of substituted DTF. It involves first the formation of the cation radical which couples to form the protonated dication. This dication slowly deprotonates to give the final TTF (k=0.5-1 s(-1)). The dimerization rate constant was found to be in the range of k(dim)=(2-4) x 10(8) L mol(-1) s(-1) and not vary much with the nature of the substituent.
Keywords:PI-ELECTRON DONORS;ELECTROCHEMICAL OXIDATION;CONDUCTIVE COMPLEXES;SPACER GROUPS;LINEAR SWEEP;TETRATHIAFULVALENE;ANALOGS;DEPROTONATION