| Project/Area Number |
09044096
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (B).
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Inorganic chemistry
|
|---|
| Research Institution | Kumamoto University |
|---|
Principal Investigator |
SAKAKI Shigeyoshi Fac. of Eng., Kumamoto University, Professor, 工学部, 教授 (20094013)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
MUSASHI Yasuo Data Processing Center, Kumamoto University, Assistant Professor, 総合情報処理センター, 講師 (10271131)
HAMADA Taisuke Fac. of Eng., Kumamoto University, Associate Professor, 工学部, 助手 (10253717)
SUGIMOTO Manabu Graduate School of Science and Technology, Kumamoto University, Associate Professor, 大学院・自然科学研究科, 講師 (80284735)
|
|---|
| Project Period (FY) |
1997 – 1999
|
| Project Status |
Completed (Fiscal Year 1999)
|
| Budget Amount *help |
¥9,000,000 (Direct Cost: ¥9,000,000)
Fiscal Year 1999: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1998: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1997: ¥4,000,000 (Direct Cost: ¥4,000,000)
|
|---|
| Keywords | Chiral ruthenium (II) bipyridine complex / Chiral Copper (I) complex / Pulse radiolysis / Laser Flash Photolysis / Photoasymmetric reduction / Photoasymmetric synthesis / Molecular / Mechanics Study / Marcus theory / キラル銅(I)ビピリジン錯体 / キラルコバルト錯体 / 立体選択的光還元 / 静的消光反応 / ab initioMO計算 / ZINDO計算 / エネルギー移動 / 光還元反応 / 光不斉合成反応 / キラル光増感剤 / 銅(I)錯体 / ルテニウム(II)錯体 / 立体選択的光還元反応 / パルスラジオリシス / 光反応 / 立体選択反応 / コバルト錯体 / 電子移動反応 / エネルギー移動反応 |
|---|
| Research Abstract |
(1)Chiral photosensitizers, Δ-[Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 (menbpy=4,4'-bis(1R,2S,5R)-(-)menthoxycarbonyl}-2,2'-bipyridine), Δ-[Ru(phenebpy)ィイD23ィエD2]ィイD12+ィエD1 (phenebpy=4,4'-bis(1-phenethylaminocarbonyl)-2,2'-bipyridine), [Cu(tmdcbpy)(PRィイD23ィエD2)ィイD22ィエD2]ィイD12+ィエD1(tmdcbpy=4,4'-6,6'-tetramethyl-5,5'-bis(S)-(-)-1-phenylcarbamoyl-2,2'-bipyridine) were newly synthesized here. (2) Pulse radiolysis of Δ-[Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 in ethanol yields one-electron reduced species in which ruthenium(I) is not involved but anion radical of menbpy ligand is involved. Reduction of [Co(acac)ィイD23ィエD2] by this Δ-[Ru(menbpy)ィイD23ィエD2]ィイD1+ィエD1 occurs stereoselectively with selectivity of 2.7. (3) [Cu(tmdcbpy)(PPhィイD23ィエD2)]ィイD1+ィエD1 perfomrs stereoselective photoreduction of [Co(edta)]ィイD1-ィエD1 with significantly large enantiomer excess (60% at 10% conversion), under near-UV light irradiation, while [Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 cannot perform stereoselective photoreduction of [Co(edta)]
… More
ィイD1-ィエD1. (4) Photoreductions of cationic methylviologen and anionic 4,4'-bis(3-carboxyethyl)-1,1'-bipyridinium (dcbpy) by [Ru(bpy)ィイD23ィエD2]ィイD12+ィエD1 were investigated with laser flash photolysis. The reaction rate significantly depend on the electrostatic interaction; both photoinduced electron transfer from ィイD1*ィエD1[Ru(bpy)ィイD23ィエD2]ィイD12+ィエD1 to MVィイD12+ィエD1 and the reverse electron transfer from MVィイD1+ィエD1 to [Ru(bpy)ィイD23ィエD2]ィイD13+ィエD1 occur more slowly than those of dcbpy. (5) Analysis based on Marcus theory showed that the electronic coupling term HィイD2rpィエD2 significantly depends on the electrostatic interaction, suggesting that the electrostatic interaction is important to the stereoselectivity in electron transfer reaction. (5) Photoderacemization of [Co(acac)ィイD23ィエD2] was carried out with Δ-[Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 in acetonitrile-water under visible light irradiation. Quenching reactions and model reaction indicate that this reaction takes place through the oxidative quenching of Δ-ィイD1*ィエD1[Ru(menbpy)ィイD23ィエD2]ィイD12+ィエD1 by[Co(acac)ィイD23ィエD2]. (6) Electron transfer reaction was investigated with molecular mechanics, which shows that [Co(acac)ィイD23ィエD2] approaches [Ru(bpy)ィイD23ィエD2]ィイD12+ィエD1 along the CィイD23vィエD2 axis. Less
|
