| Project/Area Number |
10440192
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | Nagoya University |
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Principal Investigator |
TATSUMI Kazuyuki Nagoya University, Research Center for Materials Science, Professor, 物質科学国際研究センター, 教授 (10155096)
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| Co-Investigator(Kenkyū-buntansha) |
川口 博之 分子科学研究所, 錯体化学実験施設, 助手 (20262850)
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| Project Period (FY) |
1998 – 2000
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥13,300,000 (Direct Cost: ¥13,300,000)
Fiscal Year 2000: ¥4,400,000 (Direct Cost: ¥4,400,000)
Fiscal Year 1999: ¥4,200,000 (Direct Cost: ¥4,200,000)
Fiscal Year 1998: ¥4,700,000 (Direct Cost: ¥4,700,000)
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| Keywords | chalcogen / sulfide / selenide / tungsten / hetero-dimetallic complexes / alkylation / fluxionality / chiral separation / オキソ / アルキル化 / 不斉 / 光学分割 / モリブデン / チオラート / 炭素-硫黄、結合切断 / 不斉分割 / 反応機構 / 炭素-硫黄結合切断 / 炭素-硫黄結合生成 |
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| Research Abstract |
( 1 ) We have synthesized a series of S-bridged W-Ru and W-Rh dinuclear complexes from the reactions of the half-sandwich tungsten trisuffido complex (PPh_4)[Cp*WS_3] and various ruthenium and rhodium complexes. And reactivity of the hetero-dimetallic has been examined. For instance, we have found that the dinuclear hydride complex Cp*W(m-S)_3RuH(PPh_3)_2 reacts with 1 equiv of MeOCOC≡CH to give Cp*W(μ-S)_3Ru(C(=CH_2)COOMe)(PPh_3)_2. On the other hand, the reaction between Cp*W(S)(μ-S)_2-Rh(PPh_3)_2 and 1 equiv of MeOCOC≡CH in THFgave rise to Cp*W(μ-S_2C_2HCOOMe)(μ-S)Rh(PPh_3)_2, where the alkyne was added to the terminal S atom and the bridging S atom.
( 2 ) We carried out a series of alkylation reactions at a terminal sulfide of (PPh_4)[Cp*WS_3]. For instance, the reaction with allychloride or methallychloride produced Cp* W(S)_2(SCH_2CR=CH_2) (R = H, Me). which was found to show intresting fluxional behavior of the allylthiolate group. In order to elucidate the mechanism of the fluxionality, we have newly synthesized (PPh_4)[(EtMe_4C_5)W(O)(S)-(SCH_2CR=CH2)] and (PPh_4)[(Me_5C_5)W(O)(S) (SeCH_2CR=CH_2)], and have analyzed variable-temperature ^1H NMR spectra of these complexes. The allyl group of (PPh_4)[(EtMe_4C_5)W(O)(S)- (SCH_2CR=CH_2)] was found to migrate between the two S sites, while the 1,3-allyl shift occured at Se in the case of (PPh_4) (Me_5C_5)W(O)(S)(SeCH_2CR=CH_2)].
( 3 ) We have successfully synthesized the halfsandwich tungsten complex which carries three different chalcoge atoms, (PPh_4)[Cp*W(O)(S)(Se)]. Furthermore, we were able to separate the diastereomers of (PPh_4)[Cp*W(O)(S)(SR*)] (R* = chiral alkyl group), and the subsequent reaction with Li_2Se_2 gave enatio-excess (PPh_4)[Cp*W(O)(S)(Se)].
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