Thermal and photochemical reduction of aqueous chlorine by ruthenium(II) polypyridyl complexes

Oxidation of a series of metal complexes by aqueous chlorine yields a linear free energy relationship relating k(sub et) to E degrees, which is consistent with an outer-sphere electron-transfer mechanism. The data establishes lower limits to E degrees for the Cl2/Cl(sub 2)(super -) redox couple and for [Ru(bpy)(sub 3)](super 2+) the thermal rates are uncompetitive with the photochemical rates.