| Co-Investigator(Kenkyū-buntansha) |
SHIBATA Takanori Faculty of Science and Engineering, Professor, 理工学術院, 教授 (80265735)
NAKAI Hiromi Faculty of Science and Engineering, Professor, 理工学術院, 教授 (00243056)
KIKUTI Yasuaki Faculty of Science and Engineering, Research Assistant, 理工学術院, 助手 (00434283)
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| Research Abstract |
1,6 Coordinate perphosphoranide anion (12-P-6) are usually unstable and difficult to be isolated. In order to stabilize the anion, two equivalents of the bidentate Martin ligand (hexafluorocumyl alcohol) were reacted with phosphorus trichloride to generate 4 coordinate phosphoranide anion (10-P-4) in situ. Conjugate aldehydes and 1,2-diketones were reacted with the anion (10-P-4) to effect Diels-Alder type 1,4-cycloadditon to synthesize 6 coordinate perphosphoranide anions (12-P-6). The anion (12-P-6) was isolated stable and the structure was determined by X-ray analysis when phenanhrenequinone was used as a 1,2-diketone. Gnerally, the anions (12-P-6) were hydrolyzed to give 5 cordinate phosphoranes (10-P-5) bearing ethylene aldehyde group and the aldehydes were characterixed as their 2,4-dinitrophenylhydrazones.
2,Syntheses and structure determination by X-ray analysis of a variety of 5 coordinate hypervalent carbon species (10-C-5) were reported as full papers in the fiscal year of 20
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05. In 2006, we challenged to synthesize 6 coordinate hypervalent carbon species (12-C-6). Because of the new and unique idea to prepare 12-C-6 species, several attempts were tried. Finally, an allene compound which bears thioxanthene skeleton at the terminal 1,3-carbons was prepared and the two sulfur atoms were methylated to yield the 6 coordinate carbon species. For the methylation, only the strongest methylation reagent, i.e., carborane reagent, could lead to success. The reagent was developed by Professor C. Reed group of Riverside, California, USA.
3,Syntheses, crystal and solution structures, ligand exchange and ligand coupling reactions of mixed pentaarylantimony compounds were reported as a full paper in 2007. The experiments were quite complicated and contained a variety of aspects of hypervalent pentacoordinate compounds and had been completed several years before. By analyzing the total experimental results, it was concluded that the reaction proceeded through the two apical ligands which was termed as "memory effect". Less
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