| Project/Area Number |
06403009
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| Research Category |
Grant-in-Aid for General Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Research Field |
Inorganic chemistry
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| Research Institution | The University of Tokyo |
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Principal Investigator |
SAITO Taro The University of Tokyo, Graduate School of Science, Professor, 大学院・理学系研究科, 教授 (90011006)
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| Co-Investigator(Kenkyū-buntansha) |
IMOTO Hido The University of Tokyo, Graduate Schoool of Science, Ass.Prof., 大学院・理学系研究科, 助教授 (20168529)
KOBAYASHI Akiko The University of Tokyo, Graduate School of Science, Ass.Prof., 大学院・理学系研究科, 助教授 (50011705)
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| Project Period (FY) |
1994 – 1995
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| Project Status |
Completed (Fiscal Year 1995)
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| Budget Amount *help |
¥15,600,000 (Direct Cost: ¥15,600,000)
Fiscal Year 1995: ¥5,100,000 (Direct Cost: ¥5,100,000)
Fiscal Year 1994: ¥10,500,000 (Direct Cost: ¥10,500,000)
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| Keywords | Cluster complex / Chromium / Triethylphosphine / Chevrel phase / Mixed valence / Raft cluster / Isoelectronic analogy / トリアルキルホスフィン / 伝導性固体化合物 / 正八面体 / DV-Xα法 |
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| Research Abstract |
Treatment of a hexanuclear cluster complex [Cr_6S_8 (PEt_3) _6] with S_8 in toluene at refluxing temperatures has formed a dodecanuclear cluster complex [Cr_<12>S_<16> (PEt_3) _<10>] by abstraction of one triethylphosphine from each cluster. The dimeric cluster has a mu_4-S---->Cr and a weak Cr-Cr bonds between the cluster units, which are similar to those in the Chevrel phase compunds. The expansion of the mixed valency state of the cluster has been demonstrated in the cyclic voltammetry and magnetic measurements on the cluster complexes. Thus the dimerization can be regarded as the first step to prepare "chromium Chevrel compunds" by low temperature polymerization of molecular clusters.
Another novel dimerization of trinuclear molybdenum cluster complexes to form [Mo_6E_8Cl_6- (PEt_3) _6l (E=S,Se) has been found. The number of the cluster valence electrons in the raft-type clusters and the tetranuclear cluster complexes prepared in this study corresponds well to the number of pi-electrons in fused aromatic compounds. The meaning of this "Isoelectronic Analogy" is being studied.
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