ELLINGER, F and GIEREN, A and HUBNER, T and LEX, J and LUCCHESINI, F and MERZ, A and NEIDLEIN, R and SALBECK, J (1993) THE TETRATHIAPORPHYCENE REDOX SYSTEM - ELECTROCHEMICAL REDUCTION OF A 20-PI CYCLOPHANE TO ITS DIATROPIC 22-PI DIANION. MONATSHEFTE FUR CHEMIE, 124 (8-9). pp. 931-943. ISSN 0026-9247,
Full text not available from this repository.Abstract
The reductive carbonyl coupling (McMurry reaction) of 5,5'-diformyl-2,2'-bithiophene affords the fourfold sulfur bridged [20]annulene 5 and its [30]annulene homologue 10 in 8 and 3% yields. Coupling of 5,5''-diformyl-2,2':5',2''-terthiophene produces structurally related macrocycles, albeit in very low yields. As shown by X-ray crystallographic investigation, the bridged annulenes 5 and 10 are non-planar cyclophanes exhibiting transannular electronic interaction. The sulfur bridged [20] annulene 5 constitutes the central molecule of the tetrathiaporphycene redox system emcompassing the dicationic tetrathiaporphycene 3, the annulene 5, the 22pi dianion 8 and the two intermediate radical ion species. Compound 5 is reduced in one two-electron step giving the diatropic 22-pi dianion 8 which is characterized by cyclovoltammetry, coulometry, spectroelectrochemistry and H-1-NMR spectroscopy. By contrast, 5 fails to undergo oxidation with formation of the dicationic 18pi tetrathioporphycene.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CYCLIC VOLTAMMETRY; CHEMISTRY; MCMURRY REACTION; H-1-NMR; CRYSTAL STRUCTURE; VOLTAMMETRY; COULOMETRY; SPECTROELECTROCHEMISTRY |
| Depositing User: | Dr. Gernot Deinzer |
| Last Modified: | 19 Oct 2022 08:42 |
| URI: | https://pred.uni-regensburg.de/id/eprint/53865 |
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