Photo-Oxidation of tris(2,2’-bipyridine)-iron(II) Complex by Periodate in Aqueous Solution | Sciact - CRIS-system of Boreskov Institute of Catalysis

Photo-Oxidation of tris(2,2’-bipyridine)-iron(II) Complex by Periodate in Aqueous Solution Full article

Journal

Journal of Photochemistry and Photobiology A: Chemistry
ISSN: 1010-6030 , E-ISSN: 1873-2666

Output data

Year: 1993, Volume: 74, Number: 1, Pages: 21-29 Pages count : 9 DOI: 10.1016/1010-6030(93)80147-2

Tags

EXCITED-STATES; POLYPYRIDINE COMPLEXES; COORDINATION-COMPOUNDS; ION-PAIR; PHOTOCHEMISTRY; PHOTOPHYSICS; SPECTROSCOPY; IRON(II)

Authors

Gerasimov Oleg V. ¹ , Parmon Valentin N. ¹ , Lymar Sergei V. ^1,2

Affiliations

1	Boreskov Institute of Catalysis, Russian Academy of Sciences, Pr. akademika Lavrenteva 15, 630090 Novosibirsk
2	Department of Chemical and Biologicai Sciences, Oregon Graduate Institute of Science and Technology

Thermal and photochemical oxidations of Fe(bpy)32+ (bpy = 2,2'-bipyridine) by the periodate anion IO4- in acidic aqueous solution were studied. For the thermal process, the rate-limiting step is monomolecular dissociation of the iron(II) complex preceding the fast oxidation by IO4-. Photo-oxidation of Fe(bpy)32+ by IO4- is reported for the first time. The dependence of apparent quantum yield upon IO4- concentration favours a static mechanism, which includes outer-sphere complex [Fe(bpy)32+...IO4-] formation. The complex formation has an equilibrium constant 38 +/- 11 mol-1 dm3 and is accompanied by an approximate 1 nm bathochromic shift of the metal-to-ligand charge transfer band of Fe(bpy)32+. The complex [Fe(bpy)32+...IO4-] is believed to undergo irreversible intramolecular electron transfer upon excitation with the efficiency (0.45 +/- 0.1)%. In contrast with IO4-, the persulphate anion (S2O82-) does not show any activity in the photo-oxidation of Fe(bpy)32+. This surprising specificity is explained in terms of the difference between the sizes and geometries of the oxidizing anions; the small IO4 penetrates between bipyridine ligands and reaches the internal d-orbitals of Fe(bpy)32+ from where the electron is transferred, but the bulkier S2O82- has no access to the Fe d-shell.

Gerasimov O.V. , Parmon V.N. , Lymar S.V.
Photo-Oxidation of tris(2,2’-bipyridine)-iron(II) Complex by Periodate in Aqueous Solution
Journal of Photochemistry and Photobiology A: Chemistry. 1993. V.74. N1. P.21-29. DOI: 10.1016/1010-6030(93)80147-2 WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Jul 7, 1992
Accepted:	Mar 18, 1993
Published print:	Aug 15, 1993
Published online:	Feb 5, 2002

Web of science:	WOS:A1993LV15700005
Scopus:	2-s2.0-0040311627
Elibrary:	31182856
Chemical Abstracts:	1993:591753
Chemical Abstracts (print):	119:191753
OpenAlex:	W2054781551

DB	Citing
Web of science	4
Scopus	6
Elibrary	5
OpenAlex	5