| Budget Amount *help |
¥4,200,000 (Direct Cost: ¥4,200,000)
Fiscal Year 1999: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 1998: ¥2,400,000 (Direct Cost: ¥2,400,000)
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| Research Abstract |
1. Dehydroannulenes Annelated with Bicyclooctene Frameworks.
Dehydro-[12]-, -[16]-, -[18]-, -[24]-, and -[30]-annulenes annelated with bicyclo-[2.2.2] octene (abbreviated as BCO) were synthesized and their redox behaviors investigated. Particularly the [16] annulene was found to form a stable complex with silver(I)ion, which structure was clarified by X-ray crystallography.
2. Benzenoid Aromatic Hydrocarbons Annelated with BCO.
Benzene, naphthalene, biphenylene, and anthracene fully annelated with BCO were synthesized and transformed into the first stable salts of the radical cations. The structures were determined by X-ray crystallography, and were interpreted by theoretical calculations. The radical cations were further oxidized to dications except the benzene derivative.
3. Silacycloheptatriene and Silatropylium Ion Annelated with BCO.
A series of silacycloheptatrienes tris-annelated with BCO and having various substituents on Si were synthesized and their dynamic behavior clarified by the NMR method. The derivative having a mesityl group on Si was successfully transformed into the first silatropylium ion in dichloromethane solution at low temperature. The silylium-ion character was demonstrated by the ィイD11ィエD1H, ィイD113ィエD1C, and ィイD129ィエD1Si NMR spectroscopy.
4. Sulfur-Containing Cyclic Pi-Systems Annelated with BCO.
The 1,2-and 1,4-dithiins and a thiophene annelated with two BCO units were synthesized and transformed into stable salts of the radical cations. The dithiins were further oxidized to dications, which were found to be the 6-pi electronic aromatic systems. A thiphene annelated with BCO at 3,4-positions was synthesized and transformed into the polythiophene derivative.
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