If E 0' of the organic substrate is positive of E 0' (CO2/CO2 •-) = -2.68 V vs E 0' of Fc/Fc + in DMF, then SET from CO2 •-to the organic substrate is thermodynamically allowed. Alternatively, if E 0' of the organic substrate is negative of E 0' (CO2/CO2 •-), SET is thermodynamically prohibited. In the latter scenario, CO2 •-may act as a nucleophile to a sufficiently electrophilic organic substrate, as is the case for unsaturated C-C bonds.