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.
Zhang
Hua
H
Department of Chemistry, University of California, Irvine, California 92697, USA.
Chen
Jie
J
Tomov
Ivan V
IV
Dvornikov
Alexander S
AS
Rentzepis
Peter M
PM
D003035:Cobalt / Q000737:chemistry*; D004583:Electrons; D005290:Ferric Compounds / Q000737:chemistry*; D007700:Kinetics; D010084:Oxidation-Reduction; D010777:Photochemistry; D012997:Solvents / Q000737:chemistry*; D013057:Spectrum Analysis
D005290:Ferric Compounds; D012997:Solvents; D003035:Cobalt