| Project/Area Number |
11440185
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (B)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Organic chemistry
|
|---|
| Research Institution | Tohoku University |
|---|
Principal Investigator |
KIRA Mitsuo Tohoku University, Department of Chemistry, Professor, 大学院・理学研究科, 教授 (40004452)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
IWAMOT Takeaki Tohoku University, Department of Chemistry, Instructor, 大学院・理学研究科, 助手 (70302081)
|
|---|
| Project Period (FY) |
1999 – 2001
|
| Project Status |
Completed (Fiscal Year 2001)
|
| Budget Amount *help |
¥14,800,000 (Direct Cost: ¥14,800,000)
Fiscal Year 2001: ¥2,400,000 (Direct Cost: ¥2,400,000)
Fiscal Year 2000: ¥2,400,000 (Direct Cost: ¥2,400,000)
Fiscal Year 1999: ¥10,000,000 (Direct Cost: ¥10,000,000)
|
|---|
| Keywords | stable silylene / stable disilene / photochemistry / disilabicyclobutane / inverted sigma bond / spiropentasiladiene / transition metal complex / silatriafulvene / ジリチオジシラン / ジシレン白金錯体 / シクロトリシレン / スピロ共役 / シリレンラジカルアニオン / シラシクロヘプタトリエン / 光反応 |
|---|
| Research Abstract |
The aim of our study has been to synthesize novel stable group-14 element unsaturated compounds and to reveal their structure and reactions.
The following are the major results: (1) Unusual reactions of stable dialkylsilylene with dichloromethane and chloromethylcyclopropane were discovered. The results were explained by invoking the ambiphilic nature of silylene. (2) The reactions of the electronically excited silylene with benzene derivatives were first observed. The excited silylene should have the nature of the singlet 1,1-biradical. (3) An apparent discrepancy for the dimer structure of bis(diisopropyl-amino)silylene between experiment and theory was solved by the detailed theoretical study. (4) Rates and mechanism of the E,Z-isomerization in tetrakis(trialkylsilyl)disilenes were revealed. (5) Unique mechanisms of the reactions of disilenes with alcohols and chloroalkanes were proposed on the basis of the theoretical and experimental studies. (6) A new silyllithium reagent, a 1,2-d
… More
ilithiodisilane (1), was prepared by the reaction of a tetrakis(trialkylsilyl)disilene with lithium in THF. (7) A 1,3-disilabicyclo[1.1.0]butane was synthesized using the reaction of the 1,2-dilithio-disilane 1 with a ketone. The disilabicyclobutane was found to have a unique inverted σ bridge bond. (8) A disilene-platinum complex, which has a metallacyclopropane type structure, was synthesized using the reaction of 1 with a dichloroplatinum and its structure was determined by X-ray crystallography. (9) A silicon-bowtie compound (spiropentasiladiene), whose carbon analogs have never been isolated, was first synthesized. The unique spiro-conjugation in the molecule was revealed by X-ray crystallography and theoretical calculations. (10) A stable 4-silatriafulvene having an Si=C bond with inverted polarity was synthesized and characterized by X-ray crystallography and various spectroscopies.
All these results will contribute to construct a new concepts of structure and bonding in the chemistry of main-group elements and to offer the basic structures for the future functional materials. Less
|
