Kowalski, Konrad and Karpowicz, Rafal and Mloston, Grzegorz and Miesel, Dominique and Hildebrandt, Alexander and Lang, Heinrich and Czerwieniec, Rafal and Therrien, Bruno (2015) Synthesis and (spectro) electrochemistry of mixed-valent diferrocenyl-dihydrothiopyran derivatives. DALTON TRANSACTIONS, 44 (13). pp. 6268-6276. ISSN 1477-9226, 1477-9234
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Three novel diferrocenyl complexes were prepared and characterised. 2,2-Diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran (1, sulphide) was accessible by the hetero-Diels-Alder reaction of diferrocenyl thioketone with 2,3-dimethyl-1,3-butadiene. Stepwise oxidation of 1 gave the respective oxides 2,2-diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran-1-oxide (2, sulfoxide) and 2,2-diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran-1,1-dioxide (3, sulfone), respectively. The molecular structures of 1 and 3 in the solid state were determined by single crystal X-ray crystallography. The oxidation of sulphide 1 to sulfone 3, plays only a minor role on the overall structure of the two compounds. Electrochemical (cyclic voltammetry (= CV), square wave voltammetry (= SWV)) and spectroelectrochemical (in situ UV-Vis/NIR spectroscopy) studies were carried out. The CV and SWV measurements showed that an increase of the sulphur atom oxidation from -2 in 1 to + 2 in 3 causes an anodic shift of the ferrocenyl-based oxidation potentials of about 100 mV. The electrochemical oxidation of 1-3 generates mixed-valent cations 1(+)-3(+). These monooxidised species display low-energy electronic absorption bands between 1000 and 3000 nm assigned to IVCT (= Inter-Valence Charge Transfer) electronic transitions. Accordingly, the mixed-valent cations 1(+)-3(+) are classified as weakly coupled class II systems according to Robin and Day.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | METAL-METAL INTERACTIONS; ONE-ELECTRON OXIDATION; ORGANOMETALLIC ELECTROCHEMISTRY; 5-MEMBERED HETEROCYCLES; DELTA-E-1/2 VALUES; VINYL RUTHENIUM; MOLECULAR WIRES; COMPLEXES; SYSTEMS; DELOCALIZATION; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 01 Aug 2019 11:28 |
| Last Modified: | 01 Aug 2019 11:28 |
| URI: | https://pred.uni-regensburg.de/id/eprint/6277 |
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