1991 Fiscal Year Final Research Report Summary
Syntheses and Properties of Higher Dimensional Metal Cluster Complexes
| Project/Area Number |
02453037
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
無機・錯塩・放射化学
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| Research Institution | The University of Tokyo |
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Principal Investigator |
SAITO Taro Professor The University of Tokyo Department of Chemistry, Faculty of Science, 理学部, 教授 (90011006)
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| Co-Investigator(Kenkyū-buntansha) |
KOBAYASHI Akiko Assistant The University of Tokyo Department of Chemistry, Faculty of Science, 理学部, 助手 (50011705)
IMOTO Hideo Lecturer The University of Tokyo Department of Chemistry, Faculty of Science, 理学部, 講師 (20168529)
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| Project Period (FY) |
1990 – 1991
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| Keywords | Cluster / Molybdenum / Trimethylphosphine / Triethylphosphine / Sulfide / DVXalpha / Cluster Condensation / Degenite |
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| Research Abstract |
The purpose of the present research is the preparation of conducting metal cluster compounds by solution methods. The basic reactions are condensation of smaller cluster complexes by removal of a part of sulfur atoms from the S_2 ligands in the cluster units.
When (NH_4)_2Mo_3S(S_2)_6 1 Was reacted with Na_2SO_3 in aqueous solutions, a black product was obtained. Heating of the product at 300ﾟC formed a semiconducting material. Similar reactions in the presence of copper sulfate formed a semi-conductor. It transformed into digenite Cu_9S_5, at 700ﾟC.
The reaction of 1 with trialkylphosphines in THF yielded [Mo_3S_5(PMe_3)_6] 2, [Mo_4S_6(SH)_2(PMe_3)_6] 3, and [Mo_6S_<12>(PEt_3)_6] 4.2 is an equilateral triangular cluster complex which is the first member of the series of cluster units Mo_<3n>S_<3n+2> found in the superconducting Chevrel phases. The DVXa calculations have shown the reason why the triangle is not distorted. 3 has a raft structure with a regular rhomboid shape. The peripheral Mo-Mo distances are equal and the DVXalpha calculations are consistent with the number of cluster valence electrons of 10.4 has also a raft with two fused triangles. This is the first example of molybdenum sulfide formed by the horizontal condensation of two trinuclear cluster units.
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