| Project/Area Number |
09440223
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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 | Tohoku University |
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Principal Investigator |
OGINO Hiroshi Tohoku University, Graduate School of Science, Professor, 大学院・理学研究科, 教授 (00004292)
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| Co-Investigator(Kenkyū-buntansha) |
INOMATA Shinji Fukushima University, Faculty of Education, Associate Professor, 教育学部, 助教授 (50241518)
UENO Keiji Tohoku University, Graduate School of Science, Research Associate, 大学院・理学研究科, 助手 (20203458)
TOBITA Hiromi Tohoku University, Graduate School of Science, Associate Professor, 大学院・理学研究科, 助教授 (30180160)
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| Project Period (FY) |
1997 – 1998
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| Project Status |
Completed (Fiscal Year 1998)
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| Budget Amount *help |
¥13,100,000 (Direct Cost: ¥13,100,000)
Fiscal Year 1998: ¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 1997: ¥10,200,000 (Direct Cost: ¥10,200,000)
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| Keywords | SILYLENE COMPLEX / SILYL (SILYLENE) COMPLEX / BIS (SILYLENE) COMPLEX / GERMYLENE COMPLEX / 1,3-MIGRATION / CATALYTIC REACTION / REDISTRIBUTION REACTION / METHYLATION / シリリン錯体 |
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| Research Abstract |
(1) Using tungsten as a central metal, donor-bridged bis(silylene) complexes, external donor-stabilized silyl(silylene) complexes, dimeric silyl(silylene) complexes in which the oxygen atoms of carbonyl ligands are mutually coordinated to the silylene ligands to form an eight-membered ring, and donor-free germyl(germylene) complexes were synthesized by photolysis of carbonyl complexes. The structures of these complexes have been determined by X-ray crystallography. 1,3-Migration of substituents was demonstrated to occur on isolated silyl(silylene) complexes.
(2) Reactivity of bis(silylene)ruthenium complexes was studied, and high electrophilicity of silylene ligands was proved based on their high reactivity toward alcohols and water, and the intramolecular C-H bond activation by the Si-Ru double bond. Dimethylsilylene was found to add to bis(silylene)ruthenium and iron complexes to give disilanyl(silylene) complexes.
(3) By means of iridium complexes having a (phosphinoethyl)silyl ligand, we found the following new reactions ; redistribution of substituents on hydrodisilanes, formation of SiR(Me)H2 by transfer of a methyl group from a methyl(hydrido)iridium complex to RSiH3, formation of a hydrido(silylene) complex via 1,2-hydrogen sift from a hydrosilyl ligand to a coordinatively unsaturated metal center, etc.
(4) We newly prepared some donor-stabilized cationic germylene complexes and diiron and iron-tungsten complexes bridged by a secondary alkyl-substituted silylene ligand.
(5) The first 1 , 2-phenylenedioxysilyl iron complex was synthesized, the structure determined, and the reactivity investigated.
(6) As the new reactions of silyl(carbonyl)iron complexes, we found the reaction with LiAlH_4 leading the reduction of a CO ligand and coupling with a silyl group. to give a methylsilane, and the reaction with trialkylphosphites giving acyl complexes.
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