Photo-Oxidation of tris(2,2’-bipyridine)-iron(II) Complex by Periodate in Aqueous Solution Научная публикация
| Журнал |
Journal of Photochemistry and Photobiology A: Chemistry
ISSN: 1010-6030 , E-ISSN: 1873-2666 |
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| Вых. Данные | Год: 1993, Том: 74, Номер: 1, Страницы: 21-29 Страниц : 9 DOI: 10.1016/1010-6030(93)80147-2 | ||||
| Ключевые слова | EXCITED-STATES; POLYPYRIDINE COMPLEXES; COORDINATION-COMPOUNDS; ION-PAIR; PHOTOCHEMISTRY; PHOTOPHYSICS; SPECTROSCOPY; IRON(II) | ||||
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| Организации |
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Реферат:
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.
Библиографическая ссылка:
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 CAPlusCA OpenAlex
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 CAPlusCA OpenAlex
Даты:
| Поступила в редакцию: | 7 июл. 1992 г. |
| Принята к публикации: | 18 мар. 1993 г. |
| Опубликована в печати: | 15 авг. 1993 г. |
| Опубликована online: | 5 февр. 2002 г. |
Идентификаторы БД:
| Web of science: | WOS:A1993LV15700005 |
| Scopus: | 2-s2.0-0040311627 |
| РИНЦ: | 31182856 |
| Chemical Abstracts: | 1993:591753 |
| Chemical Abstracts (print): | 119:191753 |
| OpenAlex: | W2054781551 |