Mechanistic Investigations of Photoinduced Oxygenation of Ru(II) Bis-bipyridyl Flavonolate Complexes
| Autor: | Lauren M. Harris, Kevin K. Klausmeyer, Amanda Hoogerbrugge, Patrick J. Farmer, Mukunda M. Ghimire, Mohammad A. Omary, Murugaeson R. Kumar, Xiaozhen Han |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
010405 organic chemistry
Chemistry chemistry.chemical_element 010402 general chemistry Ring (chemistry) Electrochemistry 01 natural sciences Oxygen Medicinal chemistry Pyrone 0104 chemical sciences Enzyme catalysis Reaction product Inorganic Chemistry chemistry.chemical_compound Reactivity (chemistry) Photochemical reactivity Physical and Theoretical Chemistry |
| Zdroj: | Inorganic Chemistry. 57:2416-2424 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.7b01384 |
| Popis: | We previously reported that a Ru-bound flavonolate model of flavonol dioxygenases, [RuII(bpy)2(3-hydroxyfla)][PF6], photochemically reacts with dioxygen in two different manners. Broad-band excitation generates mixtures of products characteristic of 1,3-addition of dioxygen across the central pyrone ring, as is observed in enzymatic reactions. However, low temperature excitation at wavelengths longer than 400 nm generates a unique Ru-bound 2-benzoatophenylglyoxylate product resulting from a 1,2-dioxetane intermediate. Herein, we investigate this reactivity in a series of Ru(II)bis-bipyridyl flavonolate complexes [RuII(bpy)2(3-hydroxyflaR)][PF6] (bpy = 2,2′-bipyridine; fla = flavonolate; R = p-OMe (1), p-Me (2), p-H (3), p-Cl (4)), and [RuII(bpy)2(5-hydroxyfla)][PF6] (5). The complexes’ structures, photophysical and electrochemical properties, and photochemical reactivity with oxygen were investigated in detail. Two different reaction product mixtures, from 1,2- and 1,3-additions of dioxygen, are observed ... |
| Databáze: | OpenAIRE |
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