| Budget Amount *help |
¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 2000: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1999: ¥1,800,000 (Direct Cost: ¥1,800,000)
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| Research Abstract |
Several 1,3-dithia-2-silacyclopent-4-ene (dithia-silole) derivatives were prepared by the reactions of cis-NaS-HC=CH-SNa with the corresponding dichlorosilanes. The compounds formed charge-transfer (CT) complexes with tetracyanoethylene in CH_2Cl_2. The UV-Vis spectra of the CT complexes indicated that the ionization potential of 2,2-bis (trimethylsilyl) dithiasilole was smaller than that of 2,2-dimethyldithiasilole. The results were explained by the σ(SiR)-πinteractions resulting in a higher HOMO level. Ab initio MO calculations supported the experimental results.
The reaction of 1,2-di-t-butyl-4,4-bis (t-butyldimethylsilyl)-4-silatriafulvene, which we have isolated as the first stable 4-silatriafulvene derivative, with di-t-butylcyclopropenone at 70℃ gave 1-silabicyclo [3.2.0] heptatriene unusually as pale yellow crystals (mp 122℃) in quantitative yield. The highly strained structure of the product was determined by X-ray crystallography.
A series of 2-silyl- and 2-disilanyl-substituted 2-aryl-1,3-dithiane derivatives were prepared by the reactions of 2-aryl-2-lithio-1,3-dithianes with the corresponding chlorosilanes. Photolysis of 2-phenyl-2-(pentamethyldisilanyl)-1,3-dithiane resulted in the intermediary formation of 1,1-dimethyl-2-phenyl-2-(trimethylsilyl)-2-silaethene.
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