| Project/Area Number |
62470083
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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 |
Synthetic chemistry
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| Research Institution | The University of Tokyo |
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Principal Investigator |
HIDAI Masanobu Fac. of Eng., Univ. of Tokyo; Professor, 工学部, 教授 (60011011)
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| Co-Investigator(Kenkyū-buntansha) |
MIZOBE Yasushi Fac. of Eng., Univ. of Tokyo; Research Associate, 工学部, 助手 (40175609)
YANO Shigenobu Fac. of Sci., Nara Women's Univ.; Professor, 理学部, 教授 (60011186)
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| Project Period (FY) |
1987 – 1989
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| Project Status |
Completed (Fiscal Year 1989)
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| Budget Amount *help |
¥7,000,000 (Direct Cost: ¥7,000,000)
Fiscal Year 1989: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1988: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1987: ¥4,000,000 (Direct Cost: ¥4,000,000)
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| Keywords | Transition-metal / Cluster / Thiolate / Sulfide / Ruthenium / Palladium / Molybdenum / Electroconductivity / 金属-硫黄ポリマ- / ルテニウム-硫黄クラスター / 混合金属-硫黄クラスター / ルテニウム-チオラート二核錯体 / ルテニウムー硫黄クラスター・ / パラジウムーモリブデンー硫黄クラスター / 電導性 |
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| Research Abstract |
1. A series of diruthenium complexes with two or three bridging thiolate ligands, [Cp^*Ru(K-SR)_3RuCp^*]C1, [Cp^*RuC1(mu-SR)_2RuCp^*C1], [Cp^*Ru(mu-SR)_3RuCp^*], and [Cp^*Ru(mu-S-i-Pr)_2RuCp^*] Were prepared by treatment of [Cp^*RuC1_2]_2 with various thiolate compounds (Cp^* = eta^5-C_5Me_5), the structures of which were determined by the X-ray analyses or the EXAFS study. The products sharply depended upon the nature of the thiolate compounds and reaction conditions. The reactions of these complexes with CO, t-BuNC, and H_2 were also undertaken and several novel diruthenium complexes with CO, t-BuNC, and hydride ligands, [Cp^*RuCl(mu-SR)_2RuCp^*(L)]C1, [Cp^*Ru(SR)(mu-SR)_2RuCp^*(L)], [Cp^*Ru(mu-CO)( mu-SR)_2RuCp^*] and [Cp^*RuH(mu-SR)_2RuCp^*H] (L = CO, t-BuNC) were isolated and characterized.
2. The Mo-sulfido cluster [Mo_3S_4(H_2O)_9]^<4+> reacted with Pd powder in diluted hydrochloric acid for several days to give a novel Pd-Mo-sulfido cluster [Pd_2Mo_6S_8(H_2O)_<18>]^<8+>. The double cubane structure with the bridging Pd-S bonds between two PdMo_3S_4 cores was demonstrated by the X-ray analysis. Treatment of the blue solution of this cluster in methanol with olefins such as ethylene and 1,5-cyclooctadiene resulted in the rapid color change to red, whereas analogous treatment with acetylenes such as PhC2 XI CPh and 2-butyne also afforded red solutions but much more slowly. ^1H NMR study in methanol-d_4 disclosed the coordination of ethylene presumably at the Pd site in this cluster.
3. Polymeric transition metal-sulfur compounds including [Fe_4S_4]^<2+> or [Cp^*_22Ru_2]^<4+> cores linked by m- or p-benzenedithiolate ligands were prepared by the reactions of [Fe_4S_4(S-t-Bu)_4]^<2-> or [Cp^*RuC1_2]_2 with corresponding benzenedithiols. The disks prepared from these compounds-in'solid form showed the electroconductivities included in the range of those for semiconductors.
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