Cibulka, Radek and Vasold, Rudolf and Koenig, Burkhard (2004) Catalytic photooxidation of 4-methoxybenzyl alcohol with a flavin-zinc(II)-cyclen complex. CHEMISTRY-A EUROPEAN JOURNAL, 10 (24). pp. 6223-6231. ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)Abstract
Flavin-zinc(II)-cyclen 10 contains a covalently linked substrate binding site (zinc(II)-cyclen) and a chromophore unit (flavin). Upon irradiation, compound 10 effectively oxidizes 4-methoxybenzyl alcohol (11-OCH3) to the corresponding benzaldehyde both in water and in acetonitrile. In the presence of air, the reduced flavin 10-H-2 is reoxidized, and so catalytic amounts of 10 are sufficient for alcohol conversion. The mechanism of oxidation is based on photoinduced electron transfer from the coordinated benzyl alcohol to the flavin chromophore. This intramolecular process provides a much higher photooxidation efficiency, with quantum yields 30 times those of the comparable intermolecular process with a flavin chromophore without a binding site. For the reaction in buffered aqueous solution a quantum yield of Phi = 0.4 is observed. The turnover number in acetonitrile is increased (up to 20) by high benzyl alcohol concentrations. The results show that the covalent combination of a chromophore and a suitable binding site may lead to photomediators more efficient than classical sensitizer molecules.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | PHOTOINDUCED ELECTRON-TRANSFER; TRANSITION-METAL-COMPLEXES; IODOXYBENZOIC ACID IBX; AEROBIC OXIDATION; SUPRAMOLECULAR ASSEMBLIES; BENZYL ALCOHOLS; ENERGY-TRANSFER; MILD OXIDATION; CROWN RING; EFFICIENT; electron transfer; flavin; macrocyclic ligands; photooxidation; sensitizers |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Lehrstuhl Prof. Dr. Burkhard König |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 21 Jun 2021 09:22 |
| Last Modified: | 21 Jun 2021 09:22 |
| URI: | https://pred.uni-regensburg.de/id/eprint/36864 |
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