Photoelectron detachment and solvated electron dynamics of the cobalt(III) and iron(III) oxalato complexes.

The photochemical redox reaction kinetics of [M(III)(C(2)O(4))(3)](3-) [M = Co, Fe] complexes have been reexamined and studied by time-resolved spectroscopy. The redox mechanisms of the two systems, Co and Fe, were found to be similar to each other, and solvated electrons were observed immediately after 266/267 nm photoexcitation. A reaction mechanism is proposed that involves photoelectron detachment as a primary process. The charge-transfer bands for both complexes, which had been attributed to ligand to metal charge-transfer (LMCT) transitions previously, are reassigned to charge transfer to solvent (CTTS) transitions.