| Project/Area Number |
07404053
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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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, Graduate School of Science, Professor, 大学院理学研究科, 教授 (10155096)
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| Co-Investigator(Kenkyū-buntansha) |
KAWAGUCHI Hiroyuki Nagoya University, Graduate School of Science, Assistant, 大学院理学研究科, 助手 (20262850)
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| Project Period (FY) |
1995 – 1997
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| Project Status |
Completed (Fiscal Year 1997)
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| Budget Amount *help |
¥5,300,000 (Direct Cost: ¥5,300,000)
Fiscal Year 1997: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1996: ¥2,800,000 (Direct Cost: ¥2,800,000)
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| Keywords | Molybdenu / Tungsten / Tantalum / Iron / Copper / Sulfide / Cluster / C-S Bond Cleavag / 銅 / スルフィド錯体 / セレンド錯体 / チオラート錯体 / ペンタメチルシクロペンタジェニル |
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| Research Abstract |
We herewith summarize the results obtained under this research project.
(1) A new lanthanide chemistry has been developed based on "hard" - "soft" interactions between lanthanide metals and S-donor ligands. We have isolated and structurally characterized [Li(thf)_2]_3[Yb_5S_3(S^tBu)_<12>] and [Li(tmeda)]-[YbCl_3(STsi)(tmeda)].
(2) A series of Ta/Fe chalcogenide clusters have been synthesized, which have a common pentamethyl-cyclopentadienyl tantalum fragment. The reactions of "Cp^<**>Ta(S)_3Li_2" with iron chlorides produced (Et_4N)_2 [(Cp^<**>TaS_3)_2Fe] and Ta_2Fe_4E_9 (E=S,Se), the latter of which has a cluster framework closely related to the FeMo-Co structure.
(3) The reactions of Cp^<**>TaCl (S^tBu) with hydrazines gave rise to Cp^<**>TaS (S^tBu) (eta^2-NMeNMeH) and Cp^<**>TaS (S^tBu) (eta^1-NNMe_2^tBu). Interestingly the latter complex contains a very rare amine-imide ligand.
(4) We have carried out low temperature (100^4) solid state syntheses, in order to obtain new heterometallic sulfide clusters. For example, the reaction of [NH_4]_2 [MS_4] (M=Mo, W) with 2 equiv of [Cu(CH_3CN)_4] [PF_6] under the presence of 4 equiv of dppn (=Ph_2PCH_2PPh_2) in solid lead to the formation of [Cu_4(dppm)_4MS_4] [PF_6]_2 (M=Mo, W).
(5) We have synthesized a series of W/Cu clusters with high nuclearity from the reactions between (PPh_4) - [Cp^<**>W(S)_3] and Cu(I) complexes. Examples are tetra-and octa-nuclear clusters [Cp^<**>WS_3Cu_3-Br_3]_2 and (Cp^<**>WS_3)_4Cu_4, and a 1-dimensional polymer [(Cp^<**>WS_3Ag_2)_2(mu-Br)_2]_n etc.
(6) The reaction of FeCl_3 was found to promote C-S bond cleavage of [Cp^<**> Mo(StBu)_3 giving rise to a cubane cluster Cp^<**>_2Mo_2FeS_4Cl_2, which was then reacted with Li_2S_2 to generate an unusual tris-cubane cluster Cp^<**>_2Mo_2Fe_2S_4]_3(mu-S_4).
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