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

Hua Zhang; Jie Chen; Ivan V Tomov; Alexander S Dvornikov; Peter M Rentzepis

doi:10.1021/jp075526l

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

J Phys Chem A. 2007 Nov 15;111(45):11584-8. doi: 10.1021/jp075526l. Epub 2007 Oct 5.

Authors

Hua Zhang¹, Jie Chen, Ivan V Tomov, Alexander S Dvornikov, Peter M Rentzepis

Affiliation

¹ Department of Chemistry, University of California, Irvine, California 92697, USA.

PMID: 17918817
DOI: 10.1021/jp075526l

Abstract

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.

Publication types

Research Support, N.I.H., Extramural
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Cobalt / chemistry*
Electrons
Ferric Compounds / chemistry*
Kinetics
Oxidation-Reduction
Photochemistry
Solvents / chemistry*
Spectrum Analysis

Substances

Ferric Compounds
Solvents
Cobalt