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Photo-oxidation of tris(2,2'-bipyridine)-iron(II) complex by periodate in aqueous solution

✍ Scribed by Oleg V. Gerasimov; Valentin N. Parmon; Sergei V. Lymar

Publisher: Elsevier Science
Year: 1993
Tongue: English
Weight: 962 KB
Volume: 74
Category: Article
ISSN: 1010-6030
DOI: 10.1016/1010-6030(93)80147-2

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✦ Synopsis

Thermal and photochemical oxidations of Fe(bpy)sz+ (bpy=2,2'-bipyridine) by the periodate anion IO,-in acidic aqueous solution were studied. For the thermal process, the rate-limiting step is monomolecular dissociation of the iron(D) complex preceding the fast oxidation by IO,-. Photo-oxidation of Fe(bpy)s2+ by IO,-is reported for the first time. The dependence of apparent quantum yield upon IO,concentration favours a static mechanism, which includes outer-sphere complex [Fe(bpy),2+ . ..IO.'] formation. The complex formation has an equilibrium constant 38fll mol-' dm3 and is accompanied by an approximate 1 nm bathochromic shift of the metai-toiigand charge transfer band of Fe(bpy),2+. The complex [Fe@py)j2+ . ..IO.-] is believed to undergo irreversible intramolecular electron transfer upon excitation with the efficiency (0.45fO.l)%. In contrast with IO,-, the persulphate anion (S,082-) does not show any activity in the photo-oxidation of Fe(bpy)z+. This surprising specificity is explained in terms of the difference behveen the sizes and geometries of the oxidizing anions; the small IO,-penetrates between bipyridine iigands and reaches the internal d-orbitais of Fe(bpy)s2+ from where the electron is transferred, but the bulkier S,O,,'-has no access to the Fe d-shell.

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