Grant-in-Aid for Scientific Research on Priority Areas.
|Allocation Type||Single-year Grants|
|Research Institution||TOHOKU UNIVERSITY|
YOSHIFUJI Masaaki Tohoku University Graduate School of Science, Professor, 大学院・理学研究科, 教授 (90011676)
KAWASHIMA Takayuki University of Tokyo Graduate School of Science, Professor, 大学院・理学系研究科, 教授 (80011766)
SEKIGUCHI Akira University of Tsukuba Institute of Chemistry, Professor, 化学系, 教授 (90143164)
KIRA Mitsuo Tohoku University Graduate School of Science, Professor, 大学院・理学研究科, 教授 (40004452)
NAGASE Shigeru Tokyo Metropolitan University Graduate School of Science, Professor, 大学院・理学研究科, 教授 (30134901)
TOKITOH Norihiro Kyoto University Institute of Chemical Research, Professor, 化学研究所, 教授 (90197864)
安藤 亘 筑波大学, 化学系, 教授 (30008429)
|Project Period (FY)
1997 – 2000
Completed(Fiscal Year 2000)
|Budget Amount *help
¥87,000,000 (Direct Cost : ¥87,000,000)
Fiscal Year 1999 : ¥33,000,000 (Direct Cost : ¥33,000,000)
Fiscal Year 1998 : ¥26,500,000 (Direct Cost : ¥26,500,000)
Fiscal Year 1997 : ¥27,500,000 (Direct Cost : ¥27,500,000)
|Keywords||steric protection / spiropentasiladiene / aromatic compound / ineterelement double bond / multiple bond / theoretical chemistry / intramolecular coordination / pentavalent 1, 2-oxasilatanide / 5-配位1,2-オキサシレタニド / 有機リン化合物 / 結合エネルギー / 14族元素多面体 / ゲルミルカチオン / アザホスフェチジン / 擬回転異性体 / 低配位 / X線結晶構造解析 / ヘテロ元素 / インターエレメント不飽和結合 / 小員環化合物 / リン / ケイ素 / ゲルマニウム / 理論計算|
1. Desulfurization reaction of a dithioxophosphorane bearing the 2,4-di-t-butyl-6-methylphenyl group as protecting moiety gave the corresponding dithioxophosphine, which slowly trimerized to trithiatriphosphinane and isolated.
2. Photoisomerization of a 1-tris (trialkylsilyl) cyclotrisilene proceeded to give the corresponding bicyclo [1.1.0] tetrasilane, and the addition of an alcohol occurred in the anti-addition mode. Furthermore, as byproduct, the spiropentasiladiene derivative was isolated and characterized.
3. A cyclotrigermenium ion, constituting the 3-membered 2-π electron aromatic system, reacted with a bulky nucleophile to give a cyclotrigermene, unsymmetrically substituted at the saturated germanium atom. It was found that the conformation around the double bond depends on the electronic and steric effects of the substituent.
4. Thermal reaction of penta-coordinated 1,2-oxasiletanides bearing the Martin ligand were studied in the presence of acetic acid or 1, 1, 1-trifluoroethanol as proton source. 1,2-Oxasiletanides is considered to be a reaction intermediate, which serves for the Peterson reaction and the homo-Brook rearrangement depending upon the bulkiness at the 3-position as well as the acidity of the proton source.
5. Utilizing the 2,6-bis [bis (trimethylsilyl) methyl)-4-[tris (trimethylsilyl) methyl] phenyl group, a novel stibabismuthene as a double bond compound between two different group 15 elements, was prepared and characterized.
6. Taking the electronic and steric effect of substituents into account, a real triple bond compounds of silicon, disilyne, has been proposed to be stabilized, by theoretical calculation. Similarly triple bonds containing germanium, tin, and lead ware calculated as well as silanaphthalene and silabenzene.